EP0050736B1 - Ammonium salts of polymaleic acid and their application as corrosion inhibitors in mineral oils - Google Patents

Ammonium salts of polymaleic acid and their application as corrosion inhibitors in mineral oils Download PDF

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Publication number
EP0050736B1
EP0050736B1 EP81107454A EP81107454A EP0050736B1 EP 0050736 B1 EP0050736 B1 EP 0050736B1 EP 81107454 A EP81107454 A EP 81107454A EP 81107454 A EP81107454 A EP 81107454A EP 0050736 B1 EP0050736 B1 EP 0050736B1
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Prior art keywords
acid
mineral oils
polymaleic acid
acids
ammonium salts
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German (de)
French (fr)
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EP0050736A1 (en
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Knut Dr. Oppenlaender
Karl Dr. Stork
Hans-Henning Dr. Vogel
Erich Dr. Schwartz
Claus Peter Jakob
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BASF SE
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BASF SE
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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/22—Organic compounds containing nitrogen
    • C10L1/222—Organic compounds containing nitrogen containing at least one carbon-to-nitrogen single bond
    • C10L1/2222—(cyclo)aliphatic amines; polyamines (no macromolecular substituent 30C); quaternair ammonium compounds; carbamates
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/22—Organic compounds containing nitrogen
    • C10L1/222—Organic compounds containing nitrogen containing at least one carbon-to-nitrogen single bond
    • C10L1/224—Amides; Imides carboxylic acid amides, imides

Definitions

  • Oil-soluble substances must be used as inhibitors against such corrosion. In addition to a satisfactory protective effect, such substances must also have the property of not acting as an emulsifier, or acting as little as possible, so that the condensed water remains separable as quickly as possible.
  • the aim of the invention was to find substances which have both the lowest possible emulsifying action and the best possible anti-corrosive properties and which are oil-soluble.
  • C 12 to C 16 alkylammonium salts are particularly preferred, especially the mono- or dialkylammonium salts, of which monoisotridecylammonium salts are of particular industrial interest.
  • the oligomaleic acids on which the salts are based can be obtained by various methods which belong to the prior art.
  • a similar procedure is followed according to DE-OS2047340, according to which acetic anhydride and H 2 0 2 are also added to the polymerization batch.
  • a preferred method is the procedure according to DE-OS 28 40167, to which reference is expressly made here. This method makes it possible to get from hydrolyzed oligomaleic acid from maleic anhydride in a single operation, which supplies undyed products compared to the above-mentioned processes.
  • Maleic anhydride is dissolved in 1 to 5 times the molar amount (100 to 500 mol percent - based on MA) of acetic anhydride and 0.2 to 0.5 times the molar amount is added at 80 to 140 ° C, preferably 100 to 120 ° C (20- 50 mole percent, based on MA) H 2 0 2 , preferably in the form of a 30 to 50 percent aqueous solution. After the addition, the reaction takes place at 100 to 140 ° C, preferably 100 to 120 ° C, within 1 to 8 hours.
  • the H 2 0 2 can be added immediately or gradually; the hydrogen peroxide is preferably allowed to run in slowly at the temperatures mentioned, with vigorous mechanical movement of the reaction mixture.
  • the addition time is preferably 1 to 5 hours.
  • Such acids are non-oxidizing and, for example, hydrochloric acid, sulfuric acid, orthoboric acid, p-toluic acid, phosphoric acid, tartaric acid, citric acid and / or adipic acid may be mentioned.
  • Possible reducing agents are, for example, hydrazine, hydroxylamine and their salts, then hydroquinone, pyrogallol, aldehydes, such as formaldehyde, acetaldehyde or glutardialdehyde, and reducing acids, which are preferably recommended because they combine reducing power and acid action, are hypophosphorous acid, phosphorous acid sulfurous acid, then aldehyde acids such as glyoxylic acid, phenol carboxylic acids such as salicylic acid, and sugar acids such as ascorbic acid. Oxalic acid can also be used successfully as a reducing acid.
  • the salts according to the invention are obtained by simply mixing or neutralizing the oligomaleic acid obtained with one of the amines according to the definition in an equivalent ratio of 1: 1 until a pH of approximately 7 is reached.
  • the salts are hardly emulsifying, which is surprising given their oil solubility and the presence of hydrophilic groups (polymaleate anions!). It has been shown that when the carbon numbers of the amine component and the molecular weight of the polymaleic acids are exceeded or undershot, the properties of the emulsifying effect deteriorate immediately. They also work perfectly in all types of mineral oils, especially in lubricating oils anticorrosive and are at least equivalent to the products according to the state of the art and in many cases even superior.
  • Polymaleic acids in free form or as simple salts are known from US Pat. Nos. 4,105,581 and 4,018,702 and from DE-OS 28 06 342 as corrosion inhibitors.
  • these substances only work in pure aqueous systems, since they are not oil-soluble, and, in order to achieve optimal results, they require additions of phosphates or phosphonates (US Pat. No. 4,105,581 and DE-OS 28 06 342), or zinc ions (US Pat. PS 4 018 702).
  • the salts according to the invention can be added to the mineral oils in bulk or prediluted in a solvent in amounts of 100 to 10,000 ppm, preferably 100 to 500 ppm.
  • Mineral oils to which the corrosion inhibitors can be added are e.g. B. petroleum products such as gas oil, gasoline, diesel fuels, heavy and light heating oils and mineral oil lubricants.
  • the 35% H 2 0 2 is added dropwise at 105 to 110 ° C within about 5 hours.
  • the solution turns dark, but brightens again towards the end of the reaction.
  • the mixture is stirred at about 110 ° C. for about 2 hours.
  • the low-boiling components water, acetic acid
  • water, acetic acid water, acetic acid
  • 146.25 g (0.225 mol) of the polymaleic acid are dissolved in 146.25 g of water with stirring, then the pH is adjusted to 7 with 50 g to 60 ° C. with 320 g (1.61 mol) of mono-i-tridecylamine, with up to is stirred to constant pH. Development of two phases. The aqueous phase is separated off and discarded, the org. Evaporated phase in vacuo at 70 ° C and about 20 mbar to dryness.
  • steel sheets of a certain composition are immersed in the sample and left to stand in a humidity chamber for 200 h at a certain temperature. After this time, the steel sheets are visually assessed (see table) and the weight difference of the test sheets is also determined.
  • the cleaned test strips are then weighed.
  • the evaluation is carried out in comparison to the blank value.
  • the evaluation is carried out as described under a).
  • Additized fuels (petrol) are under-layered in 100 ml measuring cylinders with a standard buffer solution (pH 6.85) and shaken intensively for 2 minutes. Then, after 5 or 10 minutes, it is assessed visually in accordance with DIN 51415.
  • the emulsion (intermediate phase) can be given in ml.

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  • Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Lubricants (AREA)
  • Preventing Corrosion Or Incrustation Of Metals (AREA)
  • Anti-Oxidant Or Stabilizer Compositions (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
  • Liquid Carbonaceous Fuels (AREA)

Abstract

Salts of polymaleic acids, having molecular weights of from 200 to 1,500, with amines, of the formula <IMAGE> where R1 and R2 are identical or different and each is hydrogen, C9-C20-alkyl or C9-C20-alkenyl and R3 is C9-C20-alkyl or C9-C20-alkenyl.

Description

Wenn Mineralöle, Benzin- oder Dieselkraftstoffe mit Eisen oder eisenhaltigen Metallen in Kontakt kommen, stellt sich das Problem der Korrosion immer dann, wenn Kondenswasser zugegen ist. Solche Kondenswässer können Säuren, Sauerstoff oder Schwefelwasserstoff enthalten, welche alle empfindliche korrosive Schäden bewirken können.When mineral oils, petrol or diesel fuels come into contact with iron or ferrous metals, the problem of corrosion arises whenever condensation is present. Such condensate can contain acids, oxygen or hydrogen sulfide, all of which can cause sensitive corrosive damage.

Als Inhibitoren gegen derartige Korrosionen müssen öllösliche Stoffe eingesetzt werden. Solche Stoffe müssen neben einer befriedigenden Schutzwirkung auch die Eigenschaft besitzen, nicht oder möglichst wenig als Emulgator zu wirken, damit das Kondenswasser möglichst schnell abtrennbar bleibt.Oil-soluble substances must be used as inhibitors against such corrosion. In addition to a satisfactory protective effect, such substances must also have the property of not acting as an emulsifier, or acting as little as possible, so that the condensed water remains separable as quickly as possible.

Für solche Zwecke hat man bisher vor allem bestimmte Amide langkettiger Fettsäuren, insbesondere der Ölsäure vorgeschlagen. So werden z. B. in der DE-PS 11 72925 Umsetzungsprodukte der Stearin-oder Ölsäure mit Diethylentriamin oder ähnlichen Alkylenpolyaminen als Korrosionsschutzmittel beschrieben. Nach dem Vorschlag der US-PS 2 975 133 sollen dafür auch Ester, Amide und Ammoniumsalze von Umsetzungsprodukten dimerer ungesättigter Fettsäuren mit Maleinsäure bzw. Maleinsäureanhydrid eingesetzt werden. Alle diese Stoffe wirken zwar in Kraftstoffen oder Mineralölen antikorrosiv, jedoch wirken sie stark emulgierend, und man war daher gezwungen, noch weitere Additive zuzusetzen, die desmulgierend wirken.For such purposes, particular amides of long-chain fatty acids, especially oleic acid, have been proposed. So z. B. in DE-PS 11 72925 reaction products of stearic or oleic acid with diethylenetriamine or similar alkylene polyamines as a corrosion inhibitor. According to the proposal in US Pat. No. 2,975,133, esters, amides and ammonium salts of reaction products of dimeric unsaturated fatty acids with maleic acid or maleic anhydride should also be used for this purpose. All of these substances have an anti-corrosive effect in fuels or mineral oils, but they have a strong emulsifying effect and one was therefore forced to add other additives that have a demulsifying effect.

Das Ziel der Erfindung bestand in der Auffindung von Stoffen, die sowohl eine möglichst geringe Emulgierwirkung als auch möglichst gute antikorrosive Eigenschaften zeigen, und die öllöslich sind.The aim of the invention was to find substances which have both the lowest possible emulsifying action and the best possible anti-corrosive properties and which are oil-soluble.

Dieses Ziel wird erfindungsgemäß mit den Ammoniumsalzen von niedermolekularen Polymaleinsäuren (Oligomaleinsäuren) erreicht, wie sie im Anspruch 1 definiert sind.This aim is achieved according to the invention with the ammonium salts of low molecular weight polymaleic acids (oligomaleic acids) as defined in claim 1.

Es handelt sich somit um Salze primärer, sekundärer oder tertiärer Amine von Oligomaleinsäuren des Molgewichts von 200 bis 1 500, wobei die Alkyl- oder Alkenylreste des Amins jeweils 9 bis 20 C-Atome enthalten. Besonders bevorzugt sind C12- bis C16-Alkylammoniumsalze, vor allem die Mono- oder Dialkylammoniumsalze, von denen Monoisotridecylammoniumsalze technisch von besonderem Interesse sind.These are salts of primary, secondary or tertiary amines of oligomaleic acids with a molecular weight of 200 to 1,500, the alkyl or alkenyl radicals of the amine each containing 9 to 20 carbon atoms. C 12 to C 16 alkylammonium salts are particularly preferred, especially the mono- or dialkylammonium salts, of which monoisotridecylammonium salts are of particular industrial interest.

Die den Salzen zugrundeliegenden Oligomaleinsäuren sind nach verschiedenen Methoden erhältlich, die zum Stand der Technik gehören. Gemäß der GB-PS 1 349 969 wird z. B. Maleinsäureanhydrid (MSA) in einem inerten Lösungsmittel in Gegenwart von Acetanhydrid und H202 polymerisiert. Ähnlich verfährt man auch gemäß der DE-OS2047340, wonach ebenfalls Acetanhydrid und H202 dem Polymerisationsansatz zugefügt werden. Eine bevorzugte Methode stellt die Arbeitsweise gemäß der DE-OS 28 40167 dar, auf die hier ausdrücklich Bezug genommen wird. Diese Methode erlaubt es, in einem einzigen Arbeitsgang aus Maleinsäureanhydrid zu hydrolysierter Oligomaleinsäure zu gelangen, der gegenüber den oben genannten Verfahren unverfärbte Produkte liefert.The oligomaleic acids on which the salts are based can be obtained by various methods which belong to the prior art. According to GB-PS 1 349 969 z. B. maleic anhydride (MA) polymerized in an inert solvent in the presence of acetic anhydride and H 2 0 2 . A similar procedure is followed according to DE-OS2047340, according to which acetic anhydride and H 2 0 2 are also added to the polymerization batch. A preferred method is the procedure according to DE-OS 28 40167, to which reference is expressly made here. This method makes it possible to get from hydrolyzed oligomaleic acid from maleic anhydride in a single operation, which supplies undyed products compared to the above-mentioned processes.

Man löst Maleinsäureanhydrid in der 1 bis 5fachen molaren Menge (100 bis 500 Molprozent - bezogen auf MSA) Acetanhydrid und gibt bei 80 bis 140 °C, vorzugsweise 100 bis 120 °C die 0,2 bis 0,5 fache molare Menge (20-50 Molprozent, bezogen auf MSA) H202, vorzugsweise in Form einer 30 bis 50 prozentigen wäßrigen Lösung zu. Nach der Zugabe läuft die Reaktion bei 100 bis 140 °C, vorzugsweise 100 bis 120 °C, innerhalb 1 bis 8 Stunden ab.Maleic anhydride is dissolved in 1 to 5 times the molar amount (100 to 500 mol percent - based on MA) of acetic anhydride and 0.2 to 0.5 times the molar amount is added at 80 to 140 ° C, preferably 100 to 120 ° C (20- 50 mole percent, based on MA) H 2 0 2 , preferably in the form of a 30 to 50 percent aqueous solution. After the addition, the reaction takes place at 100 to 140 ° C, preferably 100 to 120 ° C, within 1 to 8 hours.

Die Zugabe des H202 kann sofort oder allmählich erfolgen, vorzugsweise läßt man das Wasserstoffperoxid langsam unter starker mechanischer Bewegung des Reaktionsansatzes bei den genannten Temperaturen zulaufen. Die Zugabedauer beträgt vorzugsweise 1 bis 5 Stunden.The H 2 0 2 can be added immediately or gradually; the hydrogen peroxide is preferably allowed to run in slowly at the temperatures mentioned, with vigorous mechanical movement of the reaction mixture. The addition time is preferably 1 to 5 hours.

Zur Beschleunigung der Reaktion und zur Verbesserung der Ausbeuten und der Reinheit der Polymerisate hat es sich als günstig erwiesen, dem Reaktionsansatz geringe Mengen (0,1 bis 3 Gewichtsprozent - bezogen auf MSA -, vorzugsweise 0,1 bis 2 Gewichtsprozent) einer anorganischen oder organischen Säure zuzusetzen.In order to accelerate the reaction and to improve the yields and the purity of the polymers, it has proven advantageous to add small amounts (0.1 to 3 percent by weight, based on MAA, preferably 0.1 to 2 percent by weight) of an inorganic or organic to the reaction batch Add acid.

Solche Säuren sind nichtoxidierend, und es seien beispielsweise Salzsäure, Schwefelsäure, Orthoborsäure, p-Toluolsäure, Phosphorsäure, Weinsäure, Citronensäure und/oder Adipinsäure genannt.Such acids are non-oxidizing and, for example, hydrochloric acid, sulfuric acid, orthoboric acid, p-toluic acid, phosphoric acid, tartaric acid, citric acid and / or adipic acid may be mentioned.

Ähnlich positiv wirkt sich der Zusatz von Reduktionsmitteln und vor allem von reduzierend wirkenden Säuren aus, die in den selben Mengen wie die oben genannten Säuren zugesetzt werden.The addition of reducing agents and especially reducing acids, which are added in the same amounts as the acids mentioned above, has a similarly positive effect.

Als Reduktionsmittel kommen beispielsweise Hydrazin, Hydroxylamin und deren Salze, sodann Hydrochinon, Pyrogallol, Aldehyde, wie Formaldehyd, Acetaldehyd oder Glutardialdehyd in Betracht und als reduzierende Säuren, die bevorzugt zu empfehlen sind, weil sie Reduziervermögen und Säurewirkung vereinigen, seien unterphosphorige Säure, phosphorige Säure, schweflige Säure, sodann Aldehydsäuren, wie Glyoxylsäure, Phenolcarbonsäuren, wie Salicylsäure, und Zuckersäuren, wie Ascorbinsäure zu nennen. Auch Oxalsäure ist als reduzierende Säure mit Erfolg einsetzbar.Possible reducing agents are, for example, hydrazine, hydroxylamine and their salts, then hydroquinone, pyrogallol, aldehydes, such as formaldehyde, acetaldehyde or glutardialdehyde, and reducing acids, which are preferably recommended because they combine reducing power and acid action, are hypophosphorous acid, phosphorous acid sulfurous acid, then aldehyde acids such as glyoxylic acid, phenol carboxylic acids such as salicylic acid, and sugar acids such as ascorbic acid. Oxalic acid can also be used successfully as a reducing acid.

Die erfindungsgemäßen Salze erhält man durch einfaches Abmischen bzw. Neutralisieren der erhaltenen Oligomaleinsäure mit einem der definitionsgemäßen Amine im Äquivalentverhältnis 1 : 1, bis ein pH-Wert von ca. 7 erreicht ist. Die Salze wirken kaum emulgierend, was angesichts ihrer Öllöslichkeit und der vorhandenen hydrophilen Gruppen (Polymaleat-Anionen !) überraschend ist. Es hat sich gezeigt, daß bei Über- oder Unterschreitung der Kohlenstoffzahlen der Aminkomponente und des Molgewichts der Polymaleinsäuren hinsichtlich der Emulgierwirkung eine sofortige Verschlechterung der Eigenschaften auftritt. Außerdem wirken sie in Mineralölen aller Art, vor allem in Schmierölen einwandfrei antikorrosiv und sind hier den Produkten gemäß dem Stand der Technik zumindest gleichwertig und in vielen Fällen sogar überlegen.The salts according to the invention are obtained by simply mixing or neutralizing the oligomaleic acid obtained with one of the amines according to the definition in an equivalent ratio of 1: 1 until a pH of approximately 7 is reached. The salts are hardly emulsifying, which is surprising given their oil solubility and the presence of hydrophilic groups (polymaleate anions!). It has been shown that when the carbon numbers of the amine component and the molecular weight of the polymaleic acids are exceeded or undershot, the properties of the emulsifying effect deteriorate immediately. They also work perfectly in all types of mineral oils, especially in lubricating oils anticorrosive and are at least equivalent to the products according to the state of the art and in many cases even superior.

Polymaleinsäuren in freier Form oder als einfache Salze sind zwar aus den US-PS 4 105 581 und 4 018 702 sowie aus der DE-OS 28 06 342 als Korrosionsinhibitoren bekannt. Diese Stoffen wirken aber nur in reinwäßrigen Systemen, da sie nicht öllöslich sind, und benötigen, um optimale Ergebnisse zu erbringen, Zusätze von Phosphaten oder Phosphonaten (US-PS 4 105 581 und DE-OS 28 06 342), oder Zinkionen (US-PS 4 018 702).Polymaleic acids in free form or as simple salts are known from US Pat. Nos. 4,105,581 and 4,018,702 and from DE-OS 28 06 342 as corrosion inhibitors. However, these substances only work in pure aqueous systems, since they are not oil-soluble, and, in order to achieve optimal results, they require additions of phosphates or phosphonates (US Pat. No. 4,105,581 and DE-OS 28 06 342), or zinc ions (US Pat. PS 4 018 702).

Die erfindungsgemäßen Salze können den Mineralölen in Substanz oder vorverdünnt in einem Lösungsmittel in Mengen von 100 bis 10 000 ppm, vorzugsweise 100 bis 500 ppm zugesetzt werden.The salts according to the invention can be added to the mineral oils in bulk or prediluted in a solvent in amounts of 100 to 10,000 ppm, preferably 100 to 500 ppm.

Als Lösungsmittel kommen z. B. aromatische Kohlenwasserstoffe oder aliphatische Alkohole bzw. Alkoholgemische mit 6 bis 12 C-Atomen in Betracht.As a solvent such. B. aromatic hydrocarbons or aliphatic alcohols or alcohol mixtures with 6 to 12 carbon atoms.

Mineralöle, denen die Korrosionsinhibitoren zugesetzt werden können, sind z. B. Erdölprodukte, wie Gasöl, Benzin, Dieselkraftstoffe, schwere und leichte Heizöle und Mineralölschmierstoffe.Mineral oils to which the corrosion inhibitors can be added are e.g. B. petroleum products such as gas oil, gasoline, diesel fuels, heavy and light heating oils and mineral oil lubricants.

Die nun folgenden Beispiele erläutern die Erfindung.The following examples illustrate the invention.

BeispieleExamples a) Herstellung der Oligomaleinsäurea) Preparation of the oligomaleic acid EinsatzstoffeInput materials

  • 1 000 Teile Maleinsäureanhydrid (MSA)1,000 parts of maleic anhydride (MSA)
  • 1 400 Teile Acetanhydrid1,400 parts of acetic anhydride
  • 10 Teile H3P03 10 parts H 3 P0 3
  • 857 Teile einer 35 gew.-%igen wäßrigen H2O2-Lösung.857 parts of a 35% by weight aqueous H 2 O 2 solution.
Durchführungexecution

In einem Reaktionsgefäß mit Rückflußkühler, Rührer, Tropftrichter und Innenthermometer werden MSA und der Katalysator in Acetanhydrid bei Raumtemperatur gelöst.In a reaction vessel with a reflux condenser, stirrer, dropping funnel and internal thermometer, MA and the catalyst are dissolved in acetic anhydride at room temperature.

Unter Rühren wird bei 105 bis 110°C innerhalb ca. 5 Stunden das 35%ige H202 zugetropft. Die Lösung färbt sich dabei dunkel, hellt sich aber gegen Ende der Reaktion wieder auf. Zur Beendigung der Polymerisation wird noch ca. 2 Stunden bei ca. 110°C nachgerührt.With agitation, the 35% H 2 0 2 is added dropwise at 105 to 110 ° C within about 5 hours. The solution turns dark, but brightens again towards the end of the reaction. To complete the polymerization, the mixture is stirred at about 110 ° C. for about 2 hours.

Nun werden am absteigenden Kühler die niedrig siedenden Anteile (Wasser, Essigsäure) bei ca. 30 bis 75 mbar und 120 °C Innentemperatur abdestilliert bzw. zur Trockene eingedampft. Anschließend wird im Trockenschrank getrocknet.Now the low-boiling components (water, acetic acid) are distilled off at approx. 30 to 75 mbar and 120 ° C internal temperature on the descending cooler or evaporated to dryness. Then it is dried in a drying cabinet.

Ausbeute : quantitativ, Molgewicht : ca. 650Yield: quantitative, molecular weight: approx. 650

b) Herstellung der Salzeb) Preparation of the salts Beispiel 1example 1

146,25 g (0,225 Mol) der Polymaleinsäure werden unter Rühren in 146,25 g Wasser gelöst, anschließend wird bei 50 bis 60°C mit 320 g (1,61 Mol) Mono-i-tridecylamin auf pH 7 gestellt, wobei bis zur pH-Konstanz gerührt wird. Ausbildung zweier Phasen. Die wäßrige Phase wird abgetrennt und verworfen, die org. Phase im Vakuum bei 70 °C und ca. 20 mbar zur Trockene eingedampft.146.25 g (0.225 mol) of the polymaleic acid are dissolved in 146.25 g of water with stirring, then the pH is adjusted to 7 with 50 g to 60 ° C. with 320 g (1.61 mol) of mono-i-tridecylamine, with up to is stirred to constant pH. Development of two phases. The aqueous phase is separated off and discarded, the org. Evaporated phase in vacuo at 70 ° C and about 20 mbar to dryness.

Beispiel 2Example 2

107,25 g (0,165 Mol) Polymaleinsäure werden unter Rühren in 107,25 g Wasser gelöst, anschließend wird bei 50 bis 60 °C mit 402 g (1,056 Mol) Ditridecylamin auf pH 7 gestellt, wobei bis zur pH-Konstanz gerührt wird. Ausbildung zweier Phasen. Die wäßrige Phase wird abgetrennt und verworfen, die org. Phase im Vakuum bei 70 °C und ca. 20 mbar zur Trockne eingedampft.107.25 g (0.165 mol) of polymaleic acid are dissolved in 107.25 g of water with stirring, then the pH is adjusted to 7 with 402 g (1.056 mol) of ditridecylamine at 50 to 60 ° C., stirring until the pH is constant. Development of two phases. The aqueous phase is separated off and discarded, the org. Evaporated phase in vacuo at 70 ° C and about 20 mbar to dryness.

Beispiel 3Example 3

65 g (0,1 Mol) Polymaleinsäure werden in 65 g Wasser gelöst. Anschließend setzt man 207 g eines C8- bis C12-Alkoholgemis,ches (« Oxoöl ») zu und läßt 142 g (0,715 Mol) Mono-i-tridecylamin zutropfen, wobei ein pH-Wert von ca. 7 erreicht wird. Nach einstündigem Nachrühren bei 70 bis 80 °C wird das Wasser destillativ bei 70 °C und 20 mbar entfernt.65 g (0.1 mol) of polymaleic acid are dissolved in 65 g of water. Then 207 g of a C 8 to C 12 alcohol mixture, ches (“oxo oil”) are added and 142 g (0.715 mol) of mono-i-tridecylamine are added dropwise, a pH of about 7 being reached. After stirring for one hour at 70 to 80 ° C, the water is removed by distillation at 70 ° C and 20 mbar.

Anwendungstechnische TestsApplication tests

Die Wirkung der Polymaleinate wurde nach 3 Testmethoden geprüft :The effect of the polymaleinates was tested using 3 test methods:

1. Feuchtigkeitskammer-Korrosionstest nach DIN 51 3591. Moisture chamber corrosion test according to DIN 51 359

Hierbei werden Stahlbleche bestimmter Zusammensetzung in die Probe getaucht und 200 h bei bestimmter Temperatur in einer Feuchtigkeitskammer sich selbst überlassen. Nach dieser Zeit werden die Stahlbleche optisch beurteilt (siehe Tabelle) und außerdem die Gewichtsdifferenz der Prüfbleche bestimmt.

Figure imgb0001
Here steel sheets of a certain composition are immersed in the sample and left to stand in a humidity chamber for 200 h at a certain temperature. After this time, the steel sheets are visually assessed (see table) and the weight difference of the test sheets is also determined.
Figure imgb0001

2. Grenzflächenkorrosionstest2. Interfacial corrosion test a) mit Kondenswassera) with condensed water

Je 100 ml Testöl werden mit dem zu prüfenden Inhibitor in steigenden Mengen versetzt und mit 100 ml Kondenswasser unterschichtet. Die vorbereiteten gewogenen Teststreifen werden im inhibierten Testöl durch leichtes Rühren benetzt und dann in die wäßrige Phase getaucht. Sie stehen somit zur Hälfte in der Wasserphase.

  • Versuchstemperatur : 20 bis 25 °C
  • Versuchsdauer : 18 Tage
The inhibitor to be tested is mixed with 100 ml of test oil in increasing amounts and covered with 100 ml of condensed water. The prepared weighed test strips are wetted in the inhibited test oil by gentle stirring and then immersed in the aqueous phase. Half of them are in the water phase.
  • Test temperature: 20 to 25 ° C
  • Test duration: 18 days

Die gereinigten Teststreifen werden anschließend gewogen. Die Auswertung erfolgt im Vergleich zum Blindwert.The cleaned test strips are then weighed. The evaluation is carried out in comparison to the blank value.

b) mit Schwefelwasserstoffb) with hydrogen sulfide

Die Versuche werden wie unter a) durchgeführt. In die Testflüssigkeiten wird zuerst H2S eingeleitet (30 min durchblasen)

  • Testöl : H2S-gesättigt
  • Kondenswasser: H2S-gesättigt
  • Versuchstemperatur : 20 bis 25 °C
  • Versuchsdauer : 8 Tage
The tests are carried out as under a). H 2 S is first introduced into the test liquids (blow through for 30 min)
  • Test oil: H 2 S-saturated
  • Condensed water: H 2 S-saturated
  • Test temperature: 20 to 25 ° C
  • Trial duration: 8 days

Die Auswertung erfolgt wie unter a) beschrieben.

Figure imgb0002
The evaluation is carried out as described under a).
Figure imgb0002

Hier zeigt sich vor allem die verbesserte Korrosionsschutzwirkung des erfindungsgemäßen Produkts gegenüber H2S-haltigem Wasser.This shows above all the improved corrosion protection effect of the product according to the invention compared to water containing H 2 S.

3. Emulsionstest nach DIN 51 4153. Emulsion test according to DIN 51 415

Additivierte Kraftstoffe (Benzin) werden in 100 ml Meßzylindern mit einer Standard-Pufferlösung (pH 6,85) unterschichtet und 2 Minuten intensiv geschüttelt. Anschließend wird nach 5 bzw. 10 Minuten gemäß DIN 51415 visuell bewertet. Die Emulsion (Zwischenphase) kann in ml angegeben werden.Additized fuels (petrol) are under-layered in 100 ml measuring cylinders with a standard buffer solution (pH 6.85) and shaken intensively for 2 minutes. Then, after 5 or 10 minutes, it is assessed visually in accordance with DIN 51415. The emulsion (intermediate phase) can be given in ml.

Die gebildete Trennschicht wird wie folgt bewertet :

  • (DIN 51 415)
  • 1 Klar und rein
  • 1 b Kleine, klare Bläschen
  • 2 Geringe Schlieren
  • 3 Mäßige Schlieren
  • 4 Dichte Schlieren mit starkem Schaum
    Figure imgb0003
The separation layer formed is evaluated as follows:
  • (DIN 51 415)
  • 1 Clear and pure
  • 1 b Small, clear bubbles
  • 2 low streaks
  • 3 Moderate streaks
  • 4 Dense streaks with strong foam
    Figure imgb0003

Claims (2)

1. A salt of a polymaleic acid having a molecular weight of from 200 to 1,500 and an amine, of the formula
Figure imgb0005
where R1 and R2 are identical or different and are hydrogen, C9-C20-alkyl or C9-C20-alkenyl, and R3 is C9-C20-alkyl or C9-C20-alkenyl.
2. The use of a salt of a polymaleic acid as claimed in claim 1 as a corrosion inhibitor for a mineral oil.
EP81107454A 1980-10-23 1981-09-19 Ammonium salts of polymaleic acid and their application as corrosion inhibitors in mineral oils Expired EP0050736B1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT81107454T ATE5892T1 (en) 1980-10-23 1981-09-19 AMMONIUM SALTS OF POLYMALE ACIDS AND THEIR USE AS CORROSION INHIBITORS IN MINERAL OILS.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19803039977 DE3039977A1 (en) 1980-10-23 1980-10-23 AMMONIUM SALTS OF POLYMAL ACID AND THEIR USE OF CORROSION INHIBITORS IN MINERAL OILS
DE3039977 1980-10-23

Publications (2)

Publication Number Publication Date
EP0050736A1 EP0050736A1 (en) 1982-05-05
EP0050736B1 true EP0050736B1 (en) 1984-01-18

Family

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Application Number Title Priority Date Filing Date
EP81107454A Expired EP0050736B1 (en) 1980-10-23 1981-09-19 Ammonium salts of polymaleic acid and their application as corrosion inhibitors in mineral oils

Country Status (5)

Country Link
US (1) US4435298A (en)
EP (1) EP0050736B1 (en)
AT (1) ATE5892T1 (en)
CA (1) CA1180031A (en)
DE (2) DE3039977A1 (en)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3119376A1 (en) * 1981-05-15 1982-12-02 Basf Ag, 6700 Ludwigshafen INHIBITORS AGAINST THE CORROSION OF H (DOWN ARROW) 2 (DOWN ARROW) S AND CO (DOWN ARROW) 2 (DOWN ARROW) IN WATER-IN-OIL EMULSIONS
US5599779A (en) * 1996-03-20 1997-02-04 R. T. Vanderbilt Company, Inc. Synergistic rust inhibitors and lubricating compositions
CN108949319A (en) * 2018-07-26 2018-12-07 界首市鑫龙机械设备购销有限公司 A kind of metal machinery lubricant with inhibition antiseptic property

Family Cites Families (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB828701A (en) * 1955-04-21 1960-02-24 Monsanto Chemicals Rust-inhibiting compositions and lubricants containing the same
US2975133A (en) * 1955-04-21 1961-03-14 Gulf Oil Corp Corrosion-inhibiting mineral oil compositions
US3003858A (en) * 1958-01-07 1961-10-10 Socony Mobil Oil Co Inc Stabilized distillate fuel oil
US3893825A (en) * 1970-12-30 1975-07-08 Universal Oil Prod Co Inhibition of corrosion
GB1349769A (en) 1971-11-01 1974-04-10 Fmc Corp Polymerization process
US3909215A (en) * 1973-03-27 1975-09-30 Chevron Res Rust inhibitors for hydrocarbon fuels
GB1445993A (en) 1973-06-27 1976-08-11 Exxon Research Engineering Co Lubricating oil compositions
US4018702A (en) 1974-03-11 1977-04-19 Calgon Corporation Corrosion inhibition with amine adducts of maleic anhydride polymers
US4079012A (en) 1976-10-04 1978-03-14 Bosniack David S Synthetic ester oil compositions containing organic sulfonic acid ammonium salts as load-carrying agents
US4105581A (en) * 1977-02-18 1978-08-08 Drew Chemical Corporation Corrosion inhibitor
DE2840167A1 (en) 1978-09-15 1980-03-27 Basf Ag METHOD FOR PRODUCING POLYMAL ACID ACID FROM MALE ACID ANHYDRIDE IN THE PRESENCE OF ACETANHYDRIDE AND HYDROGEN PEROXIDE

Also Published As

Publication number Publication date
EP0050736A1 (en) 1982-05-05
US4435298A (en) 1984-03-06
DE3161978D1 (en) 1984-02-23
CA1180031A (en) 1984-12-27
DE3039977A1 (en) 1982-06-03
ATE5892T1 (en) 1984-02-15

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