EP0026878B2 - Corrosion inhibitors stable in hard water - Google Patents
Corrosion inhibitors stable in hard water Download PDFInfo
- Publication number
- EP0026878B2 EP0026878B2 EP80105766A EP80105766A EP0026878B2 EP 0026878 B2 EP0026878 B2 EP 0026878B2 EP 80105766 A EP80105766 A EP 80105766A EP 80105766 A EP80105766 A EP 80105766A EP 0026878 B2 EP0026878 B2 EP 0026878B2
- Authority
- EP
- European Patent Office
- Prior art keywords
- acid
- mono
- hard water
- alkyl
- stable
- Prior art date
- Legal status (The legal status 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 status listed.)
- Expired
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F11/00—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
- C23F11/08—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids
- C23F11/10—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids using organic inhibitors
- C23F11/14—Nitrogen-containing compounds
- C23F11/145—Amides; N-substituted amides
Definitions
- alkylarylsulfonamidocarboxylic acids or their salts are proposed for this purpose.
- alkyl-substituted benzoic acids are also known.
- the types mentioned also have serious disadvantages.
- Salts of alkyl-substituted benzoic acids, for example have a strong sensitivity to water hardness, which greatly reduces their usability in the mineral oil-free cutting fluid sector, for example. Similar negative properties, but less pronounced, are also shown by alkanolamine salts of the alkylarylsulfonamidocarboxylic acids mentioned.
- N-acylaminocarboxylic acids in the form of their salts as corrosion inhibitors.
- the use of the hydrazine salts of these acids is described in SE-A 7712954.
- N-acylaminocarboxylic acids in the form of their salts with N-alkylalkylenediamines. Due to the presence of this special amine, the salts described in this document are oil-soluble and can therefore be used in systems based on liquid hydrocarbons.
- Suitable bases which are suitable for neutralizing the carboxylic acids described above are alkali metal hydroxides and alkali metal carbonates and the corresponding alkaline earth metal compounds, such as, for example, sodium hydroxide, sodium carbonate, potassium hydroxide and barium hydroxide.
- organic amines are also suitable as bases: triethanolamine, diethanolamine, triisopropanolamine, mono-, di- and triethylamine, monoisopropylamine, mono-2'-ethylcyclohexylamine, mono-i-nonylamine, 2-methyl-2'-aminopropanol, Cyclohexylamine, N, N'-dimethylcyclohexylamine, N-hexylamine, N-octylamine, triisobutylamine, di-N-hexylamine, ethylenediamine, diethylenetriamine, piperidine, piperazine or morpholine.
- the acids and the base can be used in stoichiometric amounts or in each case one component in excess.
- the claimed anti-corrosion agents can be used alone or in a mixture with known metalworking fluids or aqueous oil emulsions.
- the anti-corrosion agents can be used as aqueous solutions, -4 dispersions or emulsions.
- the application concentration in which the claimed anti-corrosion agents are used depends on the intended use of the liquid with which the ferrous and non-ferrous metals come into contact. It is generally between 0.5 and 10% by weight, preferably 2 to 5% by weight.
- it is essential that the alkyl group R of the formula given above is branched.
- aminocarboxylic acids are obtained in a known manner by reacting aminocarboxylic acids with carboxylic acid chlorides by known processes in the presence of alkali in the sense of a Schotten-Baumann reaction.
- the amino carboxylic acids are obtained, for example, by hydrolysis of lactams such as ⁇ -caprolactam or y-butyrolactam or by the addition of primary amines to acrylic acid, methacrylic acid or crotonic acid esters or nitriles and subsequent hydrolysis.
- aminocarboxylic acids are ⁇ -aminoundecanoic acid, ⁇ -aminocaproic acid, y-aminobutyric acid, ⁇ -alaninecin-Nn-butyl- ⁇ -aminopropionic acid, Ni-propyl- ⁇ -aminopropionic acid, N-cyclohexyl- ⁇ -aminopropionic acid, N-cyclohexyl-a -methyl-ß-aminopropionic acid and N-cyclohexyl- ⁇ -methyl- ⁇ -aminopropionic acid called.
- acid chlorides are pivalic acid chloride, 2-ethylhexanoic acid chloride, isononanoic acid chloride, bicycloheptenic acid chloride, tricyclodecanoic acid chloride, naphthenic acid chloride and neodecanoic acid chloride.
- Isononanoic acid chloride, 2-ethylhexanoic acid chloride and neodecanoic acid chloride are preferred.
- the salts of the carboxylic acids described above have an excellent corrosion protection effect against iron and, which is extremely important for practical use, have only a slight tendency to foam. In addition, they are very largely insensitive to the hardness constituents of the water and leave residues even under extreme electrolyte loads when drying, which can be described as low-viscosity and oily, and which do not stick. These residues can be easily dissolved with the working solution as well as with fresh water.
- the residue formation of the products obtained according to the exemplary embodiments was checked by means of a long-term pumping test.
- the principle of this test method is that around 101 of an aqueous solution of the anti-corrosive agent is pumped in large open glass vessels over a long period of time at room temperature in a way that is suitable for causing deposits on the glass wall by spraying and evaporation processes.
- an electrically operated, commercially available laboratory pump with a delivery rate of 10 l / min. introduced, which sucks the solution through a 0.8 cm diameter hose, conveys it above level and presses it back onto the surface of the bath contents in a sharp jet.
- the exit opening of the jet is approx. 15 cm above the liquid level, the entry angle of the jet can be chosen as desired.
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Preventing Corrosion Or Incrustation Of Metals (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
Im gesamten Bereich der Metallverarbeitung und Metalloberflächenbehandlung sowie in Kühlkreisläufen ist es üblich, zur Vermeidung unerwünschter Korrosionserscheinungen mehr oder minder stark alkalisch wässrige Lösungen einzusetzen, die korrosionsinhibierende Zusätze für Eisen- und Nichteisenmetalle enthalten. Dies gilt beispielsweise für so weit verbreitete Prozesse wie die spangebende und spanlose Metallumformung, die Reinigungsbehandlung von Metalloberflächen oder den Innenschutz strömender wässriger Systeme.In the entire field of metal processing and metal surface treatment as well as in cooling circuits, it is customary to use more or less strongly alkaline aqueous solutions which contain corrosion-inhibiting additives for ferrous and non-ferrous metals in order to avoid undesirable corrosion phenomena. This applies, for example, to processes as widespread as metal-cutting and non-cutting metal forming, the cleaning treatment of metal surfaces or the internal protection of flowing aqueous systems.
Bekannte und weitverbreitete korrosionsinhibierende Zusätze sind beispielsweise anorganische Salze wie Natriumnitrit oder Chromate, gegen deren weitere Verwendung auf diesen Arbeitsgebieten jedoch zunehmend toxikologische bzw. ökologische Gründe sprechen.Known and widespread corrosion-inhibiting additives are, for example, inorganic salts such as sodium nitrite or chromates, but against their further use in these fields, there are increasingly toxicological and ecological reasons.
In jüngerer Zeit weicht man deshalb auf organische Inhibitorensysteme aus, die die genannten Nachteile nicht mehr zeigen. So werden beispielsweise gemäss der DE-B 1 298672 Alkylarylsulfonamidocarbonsäuren bzw. deren Salze für diesen Zweck vorgeschlagen. Bekannt ist auch die Verwendung von alkylsubstituierten Benzoesäuren. Die genannten Typen haben aber auch schwerwiegende Nachteile. Salze der alkylsubstituierten Benzoesäuren beispielsweise besitzen eine starke Empfindlichkeit gegenüber der Wasserhärte, was die Verwertbarkeit etwa auf dem Sektor der mineralölfreien Zerspanungsflüssigkeiten stark herabmindert. Ähnliche negative Eigenschaften, jedoch geringer ausgeprägt, zeigen auch Alkanolaminsalze der angeführten Alkylarylsulfonamidocarbonsäuren. Hierbei kommt es mit zunehmender Gebrauchsdauer der Funktionsflüssigkeiten aufgrund von Verdampfungsverlusten an reinem Wasser und der damit verbundenen Aufhärtung der Gebrauchslösung zu einer Ausscheidung schwerlöslicher Calcium- bzw. Magnesiumsalze, die zur Bildung von kristallinen Rückständen auf den Maschinen und zur Verarmung der Lösung an wirksamer Substanz führt.Recently, organic inhibitor systems have therefore been switched to which no longer have the disadvantages mentioned. For example, according to DE-B 1 298672 alkylarylsulfonamidocarboxylic acids or their salts are proposed for this purpose. The use of alkyl-substituted benzoic acids is also known. The types mentioned also have serious disadvantages. Salts of alkyl-substituted benzoic acids, for example, have a strong sensitivity to water hardness, which greatly reduces their usability in the mineral oil-free cutting fluid sector, for example. Similar negative properties, but less pronounced, are also shown by alkanolamine salts of the alkylarylsulfonamidocarboxylic acids mentioned. With increasing service life of the functional liquids due to evaporation losses in pure water and the associated hardening of the working solution, there is an elimination of poorly soluble calcium or magnesium salts, which leads to the formation of crystalline residues on the machines and to the depletion of the solution of active substance.
Bekannt ist auch die Verwendung von N-Acylaminocarbonsäuren in Form ihrer Salze als Korrosionsschutzmittel. So ist in SE-A 7712954 die Verwendung der Hydrazinsalze dieser Säuren beschrieben.It is also known to use N-acylaminocarboxylic acids in the form of their salts as corrosion inhibitors. The use of the hydrazine salts of these acids is described in SE-A 7712954.
Weiterhin ist aus der DE-A 1 645745 bekannt, die N-Acylaminocarbonsäuren in Form ihrer Salze mit N-Alkyl-alkylendiaminen einzusetzen. Bedingt durch die Anwesenheit dieses speziellen Amins sind die in diesem Dokument beschriebenen Salze öllöslich und können daher in Systemen eingesetzt werden, die auf flüssigen Kohlenwasserstoffen basieren.It is also known from DE-A 1 645745 to use the N-acylaminocarboxylic acids in the form of their salts with N-alkylalkylenediamines. Due to the presence of this special amine, the salts described in this document are oil-soluble and can therefore be used in systems based on liquid hydrocarbons.
Gegenstand der vorliegenden Erfindung sind wassermischbare, hartwasserstabile Korrosionsschutzmittel, die eine Verbindung der Formel
wobei
- R, verzweigtes C6-C13-Alkyl oder C5- oder4 C6-Cycloalkyl und Polycycloalkyl mit 6 bis 13 C-Atomen, die durch 1 bis 2 C,-C4-Alkylgruppen substituiert sein können,
- R2 Wasserstoff oder C,-C6-Alkyl und
- R3 C1-C11 Alkylen in gerader oder verzweigter Kette bedeuten und diese Verbindungen in Form ihrer Alkalimetall-, Erdalkalimetall-, Triäthanolamin-, Diäthanolamin-, Triisopropanolamin-, Mono-, Di- oder Triäthylamin-, Monoisopropylamin-, Mono-2'-äthylcyclohexylamin-, Mono-i-nonylamin-, 2-Methyl-2'-aminopropanol-, Cyclohexylamin-, N,N'-dimethylcyclohexylamin-, N-Hexylamin-, N-Octylamin-, Triisobutylamin-, Di-N-hexylamin-, Äthylendiamin-, Diäthylentriamin-, Piperidin-, Piperazin- oder Morpholin-Salze vorliegen.
in which
- R, branched C 6 -C 13 alkyl or C 5 - or 4 C 6 cycloalkyl and polycycloalkyl with 6 to 13 C atoms, which can be substituted by 1 to 2 C, -C 4 alkyl groups,
- R 2 is hydrogen or C, -C 6 alkyl and
- R 3 is C 1 -C 11 alkylene in a straight or branched chain and these compounds in the form of their alkali metal, alkaline earth metal, triethanolamine, diethanolamine, triisopropanolamine, mono-, di- or triethylamine, monoisopropylamine, mono-2 'ethylcyclohexylamine, mono-i-nonylamine, 2-methyl-2'-aminopropanol, cyclohexylamine, N, N'-dimethylcyclohexylamine, N-hexylamine, N-octylamine, triisobutylamine, di-N- hexylamine, ethylenediamine, diethylenetriamine, piperidine, piperazine or morpholine salts are present.
Als Basen, die für eine Neutralisation der oben beschriebenen Carbonsäuren geeignet sind, kommen Alkalimetallhydroxide und Alkalimetallcarbonate sowie die entsprechenden Erdalkaliverbindungen in Frage, wie beispielsweise Natriumhydroxid, Natriumcarbonat, Kaliumhydroxid und Bariumhydroxid. Darüber hinaus kommen als Basen auch folgende organische Amine in Betracht: Triäthanolamin, Diäthanolamin, Triisopropanolamin, Mono-, Di- und Triäthylamin, Monoisopropylamin, Mono-2'-äthylcyclohexylamin, Mono-i-nonylamin, 2-Methyl-2'-aminopropanol, Cyclohexylamin, N,N'-dimethylcyclohexylamin, N-Hexylamin, N-Octylamin, Triisobutylamin, Di-N-hexylamin, Äthylendiamin, Diäthylentriamin, Piperidin, Piperazin oder Morpholin. Für die Salzbildung können die Säuren und die Base in stöchiometrischen Mengen oder auch jeweils eine Komponente im Überschuss verwendet werden.Suitable bases which are suitable for neutralizing the carboxylic acids described above are alkali metal hydroxides and alkali metal carbonates and the corresponding alkaline earth metal compounds, such as, for example, sodium hydroxide, sodium carbonate, potassium hydroxide and barium hydroxide. The following organic amines are also suitable as bases: triethanolamine, diethanolamine, triisopropanolamine, mono-, di- and triethylamine, monoisopropylamine, mono-2'-ethylcyclohexylamine, mono-i-nonylamine, 2-methyl-2'-aminopropanol, Cyclohexylamine, N, N'-dimethylcyclohexylamine, N-hexylamine, N-octylamine, triisobutylamine, di-N-hexylamine, ethylenediamine, diethylenetriamine, piperidine, piperazine or morpholine. For the salt formation, the acids and the base can be used in stoichiometric amounts or in each case one component in excess.
Die beanspruchten Korrosionsschutzmittel können allein oder in Mischung mit bekannten Metallbearbeitungsflüssigkeiten oder wässrigen Ölemulsionen verwendet werden. Die Korrosionsschutzmittel können als wässrige Lösungen,-4 Dispersionen oder Emulsionen angewendet werden. Die Anwendungskonzentration, in der die beanspruchten Korrosionsschutzmittel eingesetzt werden, hängt ab vom Verwendungszweck der Flüssigkeit, mit der die Eisen- und Nichteisenmetalle in Berührung kommen. Sie liegt im allgemeinen zwischen 0,5 und 10 Gew.%, vorzugsweise 2 bis 5 Gew.%. Für die Wirkung der beanspruchten Korrosionsschutzmittel ist es wesentlich, dass die Alkylgruppe R, der oben angegebenen Formel verzweigt ist. Diese Säuren erhält man in bekannter Weise durch Umsetzung von Aminocarbonsäuren mit Carbonsäurechloriden nach bekannten Verfahren in Gegenwart von Alkali im Sinne einer Schotten-Baumann-Reaktion. Die Aminocarbonsäuren gewinnt man beispielsweise durch Hydrolyse von Lactamen wie ε-Caprolactam oder y-Butyrolactam oder durch die Anlagerung primärer Amine an Acrylsäure-, Methacrylsäure- oder Crotonsäureester oder -nitrile und nachfolgende Verseifung. Als Beispiel für Aminocarbonsäuren seien Ω-Aminoundecansäure, ε-Aminocapronsäure, y-Aminobuttersäure, β-Alaninglycin-N-n-butyl-β-aminopropionsäure, N-i-Propyl-ß-aminopropionsäure, N-Cyclohexyl-ß-aminopropionsäure, N-Cyclohexyl-a-methyl-ß-aminopropionsäure und N-Cyclohexyl-β-methyl-β-aminopropionsäure genannt. Beispiele für Säurechloride sind Pivalinsäurechlorid, 2-Äthyl-hexansäurechlorid, Isononansäurechlorid, Bicycloheptensäurechlorid, Tricyclodecansäurechlorid, Naphthensäurechlorid und Neodecansäurechlorid. Bevorzugt sind Isononansäurechlorid, 2-Äthylhexansäurechlorid und Neodecansäurechlorid.The claimed anti-corrosion agents can be used alone or in a mixture with known metalworking fluids or aqueous oil emulsions. The anti-corrosion agents can be used as aqueous solutions, -4 dispersions or emulsions. The application concentration in which the claimed anti-corrosion agents are used depends on the intended use of the liquid with which the ferrous and non-ferrous metals come into contact. It is generally between 0.5 and 10% by weight, preferably 2 to 5% by weight. For the effect of the claimed anticorrosive agents, it is essential that the alkyl group R of the formula given above is branched. These acids are obtained in a known manner by reacting aminocarboxylic acids with carboxylic acid chlorides by known processes in the presence of alkali in the sense of a Schotten-Baumann reaction. The amino carboxylic acids are obtained, for example, by hydrolysis of lactams such as ε-caprolactam or y-butyrolactam or by the addition of primary amines to acrylic acid, methacrylic acid or crotonic acid esters or nitriles and subsequent hydrolysis. Examples of aminocarboxylic acids are Ω-aminoundecanoic acid, ε-aminocaproic acid, y-aminobutyric acid, β-alaninecin-Nn-butyl-β-aminopropionic acid, Ni-propyl-β-aminopropionic acid, N-cyclohexyl-β-aminopropionic acid, N-cyclohexyl-a -methyl-ß-aminopropionic acid and N-cyclohexyl-β-methyl-β-aminopropionic acid called. Examples of acid chlorides are pivalic acid chloride, 2-ethylhexanoic acid chloride, isononanoic acid chloride, bicycloheptenic acid chloride, tricyclodecanoic acid chloride, naphthenic acid chloride and neodecanoic acid chloride. Isononanoic acid chloride, 2-ethylhexanoic acid chloride and neodecanoic acid chloride are preferred.
Die Salze der oben beschriebenen Carbonsäuren besitzen eine ausgezeichnete Korrosionsschutzwirkung gegenüber Eisen und haben, was für die praktische Verwendung ausserordentlich wichtig ist, eine nur geringe Neigung zur Schaumbildung. Ausserdem sind sie sehr weitgehend unempfindlich gegenüber den Härtebildnern des Wassers und hinterlassen selbst unter extremen Elektrolytbelastungen beim Eintrocknen Rückstände, die als niedrigviskos-ölig zu bezeichnen sind, und die nicht kleben. Diese Rückstände lassen sich leicht mit der Gebrauchslösung als auch mit frischem Wasser wieder auflösen.The salts of the carboxylic acids described above have an excellent corrosion protection effect against iron and, which is extremely important for practical use, have only a slight tendency to foam. In addition, they are very largely insensitive to the hardness constituents of the water and leave residues even under extreme electrolyte loads when drying, which can be described as low-viscosity and oily, and which do not stick. These residues can be easily dissolved with the working solution as well as with fresh water.
113 g (1,0 Mol) ε-Caprolactam werden in 280 ml Wasser gelöst und mit 120 (1,0 Mol) 33-proz. Natronlauge 4 Stunden unter Stückfluss erhitzt. Man kühlt auf 20°C und tropft innerhalb 1 Stunde 158,4g (0,975 Mol) 2-Ethylhexansäurechlorid und gleichzeitig zur Aufrechterhaltung eines pH-Wertes von 12 ca. 120g 33-proz. Natronlauge bei 20-25°C zu. Die Lösung wird nachgerührt bis keine Natronlauge mehr verbraucht wird und anschliessend bei 50°C mit halkonz. Salzsäure auf pH 1 angesäuert. Man trennt in der Wärme ab und wäscht mit 350 ml Wasser. Die Säure wird am Rotationsverdampfer bei 75°C/100 ml Hg entwässert und fällt als fast farbloses viskoses Öl ab, das nach einiger Zeit kristallin erstarrt. Ausbeute 233 g (93%). Säurezahl 225, Wassergehalt 0,4%.113 g (1.0 mol) of ε-caprolactam are dissolved in 280 ml of water and with 120 (1.0 mol) 33 percent. Sodium hydroxide solution heated under piece flow for 4 hours. The mixture is cooled to 20 ° C. and 158.4 g (0.975 mol) of 2-ethylhexanoic acid chloride are added dropwise over the course of 1 hour and at the same time about 120 g of 33 percent are maintained to maintain a pH of 12. Sodium hydroxide solution at 20-25 ° C. The solution is stirred until no more sodium hydroxide solution is used and then at 50 ° C. with halkonz. Acidified to pH 1 hydrochloric acid. It is separated off in the heat and washed with 350 ml of water. The acid is dewatered on a rotary evaporator at 75 ° C / 100 ml Hg and falls off as an almost colorless viscous oil, which solidifies in crystalline form after some time. Yield 233 g (93%). Acid number 225, water content 0.4%.
Mischung aus 2-Ethyl-hexanoyl-s-aminocapronsäure und Isononanoyl-s-aminocapronsäure 113 g (1 Mol) s-Caprolactam werden wie in Beispiel 1 beschrieben hydrolysiert und anschliessend mit einer Mischung aus 79,6 g (0,49 Mol) 2-Ethylhexansäurechlorid und 86,5g (0,49 Mol) Isononansäurechlorid, die getrennt oder auch aus einer äquimolaren Mischung von 3-Ethyl-hexansäure und Isononsäure nach bekannten Verfahren hergestellt werden können, entsprechend Beispiel 1 umgesetzt. Man erhält 238,6 g (90,4%) eines fast farblosen Öls, Säurezahl216.Mixture of 2-ethyl-hexanoyl-s-aminocaproic acid and isononanoyl-s-aminocaproic acid 113 g (1 mol) of s-caprolactam are hydrolyzed as described in Example 1 and then with a mixture of 79.6 g (0.49 mol) 2 Ethylhexanoic acid chloride and 86.5 g (0.49 mol) of isononanoic acid chloride, which can be prepared separately or from an equimolar mixture of 3-ethylhexanoic acid and isononic acid by known processes, in accordance with Example 1. 238.6 g (90.4%) of an almost colorless oil, acid number 216, are obtained.
113 (1 Mol) s-Caprolactam werden gemäss Beispiel 1 hydrolysiert und mit 181,7 g (0,91 Mol) Tricyclodecansäurechlorid umgesetzt. Man erhält die Titelverbindung als gelbes hochviskoses Öl in einer Ausbeute von 236,1 g (88,5%) mit einer Säurezahl von 194.113 (1 mol) s-caprolactam are hydrolyzed according to Example 1 and reacted with 181.7 g (0.91 mol) tricyclodecanoic acid chloride. The title compound is obtained as a yellow, highly viscous oil in a yield of 236.1 g (88.5%) with an acid number of 194.
113 g (1 Mol) s-Caprolactam werden wie in Beispiel 1 hydrolysiert und mit 172 g (0,975 Mol) lsononansäurechlorid umgesetzt. Die Aufarbeitung liefert 257,5 g (95%) eines fast farblosen viskosen Öls, das nach einiger Zeit krisallin erstarrt, Säurezahl 210.113 g (1 mol) of s-caprolactam are hydrolyzed as in Example 1 and reacted with 172 g (0.975 mol) of isononyl chloride. The workup yields 257.5 g (95%) of an almost colorless viscous oil which solidifies after a while krisallin, acid number 210.
Zur Herstellung eines wässrigen Korrosionsschutzmittels wurden jeweils 35 g Säure der Beispiele 1-4 mit 50 g Triethanolamin und 15 g Wasser zu einer klaren, homogenen Lösung vermischt.To produce an aqueous corrosion inhibitor, 35 g of acid from Examples 1-4 were mixed with 50 g of triethanolamine and 15 g of water to give a clear, homogeneous solution.
Die Rückstandsbildung der nach den Ausführungsbeispielen erhaltenen Produkte wurde mittels eines Langzeit-Umpumptestes geprüft. Das Prinzip dieser Prüfmethode besteht darin, dass man ca. 101 einer wässrigen Lösung der Korrosionsschutzmittel in grossvolumigen offenen Glasgefässen über längeren Zeitraum bei Raumtemperatur in einer Weise umpumpt, die geeignet ist, auf der Glaswandung Belagbildung durch Spritz- und Verdampfungsvorgänge hervorzurufen. Zu diesem Zweck wird in die Flüssigkeit eine elektrisch betriebene, handelsübliche Laborpumpe mit einer Förderleistung von 10 I/Min. eingebracht, die durch eine Schlauchleitung von 0,8cm Durchmesser die Lösung ansaugt, über Niveau fördert und in scharfem Strahl wieder auf die Oberfläche des Badinhaltes zurückdrückt. Die Austrittsöffnung des Strahls befindet sich dabei ca. 15 cm oberhalb des Flüssigkeitsniveaus, der Eintrittswinkel des Strahls kann beliebig gewählt werden.The residue formation of the products obtained according to the exemplary embodiments was checked by means of a long-term pumping test. The principle of this test method is that around 101 of an aqueous solution of the anti-corrosive agent is pumped in large open glass vessels over a long period of time at room temperature in a way that is suitable for causing deposits on the glass wall by spraying and evaporation processes. For this purpose, an electrically operated, commercially available laboratory pump with a delivery rate of 10 l / min. introduced, which sucks the solution through a 0.8 cm diameter hose, conveys it above level and presses it back onto the surface of the bath contents in a sharp jet. The exit opening of the jet is approx. 15 cm above the liquid level, the entry angle of the jet can be chosen as desired.
Die erwünschte Belagbildung auf den nicht überspülten Teilen der Gefässwandung tritt nun auf zweierlei Weise ein. Einmal sorgt der normale Spritzvorgang für eine Benetzung. Zum anderen reisst der Strahl beim Eintauchen ständig eine Vielzahl kleinerer Luftbläschen in tiefere Schichten mit, die, an der Flüssigkeitsoberfläche wieder zerplatzend, die Gefässwandung kontinuierlich mit einem Flüssigkeitsfilm besprühen. Bei dieser Verfahrensweise ist gleichzeitig die Gewähr hoher Verdampfungsraten auch bei Raumtemperatur gewährleistet. Sie liegt bei Füllmengen von 10 I in der Grössenordnung von 1 I/Tag. Die Verluste werden jeweils durch Trinkwasser von 20 dH (ca. 350 ppm) ersetzt, wodurch eine kontinuierliche Aufhärtung des Systems erreicht wird. Die Zunahme an Härtebildnern wird hierbei rechnerisch über die jeweils zugesetzten Nachfüllmengen ermittelt.The desired formation of deposits on the parts of the vessel wall which have not been rinsed out now occurs in two ways. First, the normal spraying process ensures wetting. On the other hand, when immersed, the jet continuously entrains a large number of smaller air bubbles into deeper layers, which, again bursting at the surface of the liquid, spray the wall of the vessel continuously with a film of liquid. This procedure also guarantees high evaporation rates even at room temperature. With filling quantities of 10 I it is in the order of 1 I / day. The losses are replaced by drinking water of 20 dH (approx. 350 ppm), whereby the system is continuously hardened. The increase in hardness constituents is determined arithmetically using the replenishment quantities added.
Für die Prüfungen wurden wässrige Zubereitungen mit einem Wirkstoffgehalt von 3% verwendet. Als Vergleichsproben wurden folgende Produkte herangezogen:
- Vergleich A:
- Homogene Mischung aus
- 35% Para-tertiär-butyl-benzoesäure
- 50%Triethanolamin
- 15% H20
- Vergleich B:
- Homogene Mischung aus
- 35%s-(Benzolsulfonyl-methyl-amino)-n-capronsäure gemäss DE-C 1 298 672
- 50% Triethanolamin
- 15% H2
- Homogene Mischung aus
- Comparison A:
- Homogeneous mix of
- 35% para-tertiary-butyl-benzoic acid
- 50% triethanolamine
- 15% H 2 0
- Comparison B:
- Homogeneous mix of
- 35% s- (benzenesulfonyl-methyl-amino) -n-caproic acid according to DE-C 1 298 672
- 50% triethanolamine
- 15% H 2
- Homogeneous mix of
Die Testergebnisse sind in der nachfolgenden Tabelle zusammengefasst.
Claims (2)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE2940258 | 1979-10-04 | ||
| DE19792940258 DE2940258A1 (en) | 1979-10-04 | 1979-10-04 | HARDWATER-STABLE CORROSION PROTECTIVE |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| EP0026878A1 EP0026878A1 (en) | 1981-04-15 |
| EP0026878B1 EP0026878B1 (en) | 1983-04-06 |
| EP0026878B2 true EP0026878B2 (en) | 1987-03-11 |
Family
ID=6082698
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP80105766A Expired EP0026878B2 (en) | 1979-10-04 | 1980-09-25 | Corrosion inhibitors stable in hard water |
Country Status (11)
| Country | Link |
|---|---|
| US (1) | US4348302A (en) |
| EP (1) | EP0026878B2 (en) |
| JP (1) | JPS5658978A (en) |
| AR (1) | AR225193A1 (en) |
| BR (1) | BR8006378A (en) |
| CA (1) | CA1146589A (en) |
| CS (1) | CS216941B2 (en) |
| DE (2) | DE2940258A1 (en) |
| ES (1) | ES495437A0 (en) |
| PL (1) | PL227072A1 (en) |
| ZA (1) | ZA806124B (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5739177A (en) * | 1980-08-20 | 1982-03-04 | Ajinomoto Co Inc | Water soluble rust-resisting agent |
| FR2700336B1 (en) * | 1993-01-11 | 1995-04-14 | Hoechst France | Substituted succinimides, their preparation process and their application as corrosion inhibitor. |
| FR2738018B1 (en) * | 1995-08-24 | 1997-09-26 | Ceca Sa | INHIBITION OF CARBON CORROSION OF STEEL BY N-ALCOYL-SARCOSINES |
| DE102010010408A1 (en) * | 2010-03-05 | 2011-09-08 | Clariant International Limited | Biodegradable, frost-proof heat transfer fluid, its use in near-surface, geothermal plants, and a concentrate for its production |
| CN114539091A (en) * | 2022-03-11 | 2022-05-27 | 佛山奕安赛医药科技有限公司 | Isopalmitoylamino acid compound and preparation method and application thereof |
Family Cites Families (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| BE544208A (en) * | 1956-01-20 | 1956-07-15 | ||
| DE1545298A1 (en) * | 1965-08-28 | 1969-07-31 | Hoechst Ag | Liquid fuels |
| NO115936B (en) * | 1965-08-28 | 1968-12-30 | Hoechst Ag | |
| FR1493820A (en) * | 1965-08-28 | 1967-09-01 | Hoechst Ag | Method for combating corrosion caused by liquid fuels |
| US3484209A (en) * | 1966-12-08 | 1969-12-16 | Burndy Corp | Corrosion resistant electric contacts |
| US3857950A (en) * | 1968-05-03 | 1974-12-31 | Choay J Sa | Therapeutical composition of n-propionyl-epsilon-amino-caproic acid with method of treatment |
| US3779935A (en) * | 1971-07-12 | 1973-12-18 | Exxon Research Engineering Co | Inhibition of corrosion |
| JPS5639930B2 (en) * | 1972-04-08 | 1981-09-17 | ||
| US3878227A (en) * | 1973-12-07 | 1975-04-15 | Dow Chemical Co | Process for making tert.-butyl glycidyl ether |
| DE2758123A1 (en) * | 1977-12-24 | 1979-07-05 | Basf Ag | CORROSION PROTECTION AGENTS IN Aqueous SYSTEMS |
-
1979
- 1979-10-04 DE DE19792940258 patent/DE2940258A1/en not_active Withdrawn
-
1980
- 1980-09-25 DE DE8080105766T patent/DE3062634D1/en not_active Expired
- 1980-09-25 EP EP80105766A patent/EP0026878B2/en not_active Expired
- 1980-09-29 US US06/191,677 patent/US4348302A/en not_active Expired - Lifetime
- 1980-09-29 ES ES495437A patent/ES495437A0/en active Granted
- 1980-10-02 AR AR282757A patent/AR225193A1/en active
- 1980-10-02 CS CS806656A patent/CS216941B2/en unknown
- 1980-10-02 JP JP13682980A patent/JPS5658978A/en active Pending
- 1980-10-03 BR BR8006378A patent/BR8006378A/en unknown
- 1980-10-03 ZA ZA00806124A patent/ZA806124B/en unknown
- 1980-10-03 PL PL22707280A patent/PL227072A1/xx unknown
- 1980-10-03 CA CA000361517A patent/CA1146589A/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| PL227072A1 (en) | 1981-06-05 |
| EP0026878B1 (en) | 1983-04-06 |
| CA1146589A (en) | 1983-05-17 |
| ZA806124B (en) | 1981-09-30 |
| AR225193A1 (en) | 1982-02-26 |
| JPS5658978A (en) | 1981-05-22 |
| US4348302A (en) | 1982-09-07 |
| DE2940258A1 (en) | 1981-04-16 |
| BR8006378A (en) | 1981-04-14 |
| EP0026878A1 (en) | 1981-04-15 |
| ES8200644A1 (en) | 1981-11-01 |
| ES495437A0 (en) | 1981-11-01 |
| DE3062634D1 (en) | 1983-05-11 |
| CS216941B2 (en) | 1982-12-31 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP0046139B1 (en) | Use of triazine-carboxylic acids as corrosion inhibitors for aqueous systems | |
| EP0129506B1 (en) | Heterocyclically substituted thio(cyclo)alkane polycarboxylic acids | |
| EP0088724B1 (en) | Mixtures of benzotriazoles, process for their preparation and their use as metal passivators | |
| EP0074336A1 (en) | Systems inhibited against corrosion and/or scale formation | |
| EP0222311A2 (en) | Use of alkoxy-hydroxy-substituted fatty acids as corrosion inhibitors in oils and emulsions containing oil | |
| DE2759233A1 (en) | WATER-BASED HYDRAULIC LIQUIDS | |
| DE3137525A1 (en) | TREATMENT OF AQUEOUS ANTI-CORROSION SYSTEMS | |
| EP0026878B2 (en) | Corrosion inhibitors stable in hard water | |
| DE2453107B2 (en) | Process for the preparation of phosphoester scale and corrosion inhibiting agents, such agents and their use | |
| DE2840112C2 (en) | Water-miscible corrosion inhibitors and methods of preventing the corrosion of ferrous metals | |
| EP0029529B1 (en) | Reaction products of sulfone or carboxamido carboxylic acids with alkanol amines, and their use as corrosion inhibitors with low foam formation | |
| DE19648843C2 (en) | Melamine polycarboxamides and their use as anti-corrosion agents | |
| EP0029892B1 (en) | Use of alcali or amino salts of a mixture of 2- and 3-alkyl-adipinic acids as corrosion inhibitor | |
| DE2511400C2 (en) | Amidosulfocarboxylic acids and their salts, processes for their production and their use as corrosion protection agents | |
| WO2013139650A1 (en) | Corrosion-protection system for treating metal surfaces | |
| EP0231524B1 (en) | Application of alkylbenzoylacrylic acids as corrosion inhibitors | |
| EP0039314B1 (en) | Use of phosphoric acid di-esters as corrosion inhibitors | |
| EP1041174B1 (en) | Melamine containing corrosion inhibiting composition | |
| US4724124A (en) | Use of alkenylsuccinic acid half-amides as anti-corrosion agents | |
| EP0294687A1 (en) | Use of sulfonamidcarboxylic acid salts as corrosion inhibitors in aqueous systems | |
| DE3341633C2 (en) | ||
| EP2031094A2 (en) | Corrosion inhibitors containing anionic tensides | |
| DE3416857A1 (en) | Phenoxyalkanecarboxylic acid alkanolamine salts as water-soluble corrosion inhibitors | |
| EP0191952A1 (en) | Salts of alkenylsuccinamic acids, process for their preparation and their use as corrosion inhibitors | |
| EP0041039A1 (en) | Use of salts or partial esters of aminotriazine-carboxylic acids as corrosion inhibitors for metals in aqueous systems |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PUAI | Public reference made under article 153(3) epc to a published international application that has entered the european phase |
Free format text: ORIGINAL CODE: 0009012 |
|
| AK | Designated contracting states |
Designated state(s): BE CH DE FR GB IT NL SE |
|
| 17P | Request for examination filed |
Effective date: 19811007 |
|
| ITF | It: translation for a ep patent filed |
Owner name: ING. C. GREGORJ S.P.A. |
|
| GRAA | (expected) grant |
Free format text: ORIGINAL CODE: 0009210 |
|
| AK | Designated contracting states |
Designated state(s): BE CH DE FR GB IT LI NL SE |
|
| REF | Corresponds to: |
Ref document number: 3062634 Country of ref document: DE Date of ref document: 19830511 |
|
| ET | Fr: translation filed | ||
| PLBI | Opposition filed |
Free format text: ORIGINAL CODE: 0009260 |
|
| 26 | Opposition filed |
Opponent name: BASF AKTIENGESELLSCHAFT Effective date: 19840105 |
|
| GBPC | Gb: european patent ceased through non-payment of renewal fee | ||
| PUAH | Patent maintained in amended form |
Free format text: ORIGINAL CODE: 0009272 |
|
| 27A | Patent maintained in amended form |
Effective date: 19860820 |
|
| PUAC | Information related to the publication of a b1 document modified or deleted |
Free format text: ORIGINAL CODE: 0009299EPPU |
|
| NLR2 | Nl: decision of opposition | ||
| PUAD | Information related to the publication of a b2 document modified or deleted |
Free format text: ORIGINAL CODE: 0009399EPPU |
|
| DB1 | Publication of patent cancelled | ||
| R27A | Patent maintained in amended form (corrected) | ||
| NLXE | Nl: other communications concerning ep-patents (part 3 heading xe) |
Free format text: IN PAT.BUL.20/86,PAGE 2475:SHOULD BE DELETED |
|
| ET3 | Fr: translation filed ** decision concerning opposition | ||
| PUAH | Patent maintained in amended form |
Free format text: ORIGINAL CODE: 0009272 |
|
| STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: PATENT MAINTAINED AS AMENDED |
|
| 27A | Patent maintained in amended form |
Effective date: 19870311 |
|
| AK | Designated contracting states |
Kind code of ref document: B2 Designated state(s): BE CH DE FR GB IT LI NL SE |
|
| ITF | It: translation for a ep patent filed |
Owner name: ING. C. GREGORJ S.P.A. |
|
| NLR3 | Nl: receipt of modified translations in the netherlands language after an opposition procedure | ||
| PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: FR Payment date: 19910815 Year of fee payment: 12 |
|
| PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: CH Payment date: 19910819 Year of fee payment: 12 |
|
| PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: SE Payment date: 19910822 Year of fee payment: 12 Ref country code: GB Payment date: 19910822 Year of fee payment: 12 |
|
| PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: BE Payment date: 19910904 Year of fee payment: 12 |
|
| ITTA | It: last paid annual fee | ||
| PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: NL Payment date: 19910930 Year of fee payment: 12 |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: GB Effective date: 19920925 |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: SE Effective date: 19920926 |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: LI Effective date: 19920930 Ref country code: CH Effective date: 19920930 Ref country code: BE Effective date: 19920930 |
|
| BERE | Be: lapsed |
Owner name: HOECHST A.G. Effective date: 19920930 |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: NL Effective date: 19930401 |
|
| NLV4 | Nl: lapsed or anulled due to non-payment of the annual fee | ||
| GBPC | Gb: european patent ceased through non-payment of renewal fee |
Effective date: 19920925 |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: FR Effective date: 19930528 |
|
| REG | Reference to a national code |
Ref country code: CH Ref legal event code: PL |
|
| REG | Reference to a national code |
Ref country code: FR Ref legal event code: ST |
|
| EUG | Se: european patent has lapsed |
Ref document number: 80105766.2 Effective date: 19930406 |
|
| PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: DE Payment date: 19981113 Year of fee payment: 19 |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: DE Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20000701 |