EP0191952A1 - Salts of alkenylsuccinamic acids, process for their preparation and their use as corrosion inhibitors - Google Patents

Salts of alkenylsuccinamic acids, process for their preparation and their use as corrosion inhibitors Download PDF

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EP0191952A1
EP0191952A1 EP85116667A EP85116667A EP0191952A1 EP 0191952 A1 EP0191952 A1 EP 0191952A1 EP 85116667 A EP85116667 A EP 85116667A EP 85116667 A EP85116667 A EP 85116667A EP 0191952 A1 EP0191952 A1 EP 0191952A1
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formula
mol
salts
alkenyl
amidamine
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EP0191952B1 (en
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Werner Dr. Ritschel
Hermann Dr. Hoffmann
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Hoechst AG
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Hoechst AG
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    • 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

  • succinic acid derivatives are already known as anti-corrosion agents.
  • alkyl or alkenylsuccinic acid half esters are described in US Pat. No. 4,053,426, which are used in the form of the amine salts for lubricants and aqueous metalworking fluids.
  • US Patent 4,235,874 describes alkenyl succinic acid or anhydride and triesters of triethanolamine as corrosion inhibitors for refined petroleum products.
  • US Pat. No. 4,148,605 Ester dicarboxylic acids described, which are obtained by reacting alkenyl succinic anhydride with hydroxy carboxylic acids.
  • succinic acid half-amides are also known: for example, US Pat. No. 2,490,744 lists reaction products of alkenylsuccinic anhydrides with primary amines in a molar ratio of 1.25 to 2: 1 as rust inhibitors in lubricating oils, the total number of carbon atoms in the reaction product being between 28 and 50 should be.
  • German Offenlegungsschrift 3,300,874 alkanolamine salts of alkenylsuccinic acid half-amides are described as corrosion inhibitors for aqueous systems; these compounds are prepared by reacting alkenylsuccinic anhydrides with primary CI - Cl0 amines and subsequent neutralization with C 2 -C 4 alkanolamines.
  • Further alkenylsuccinic acid halamides and their use as corrosion protection agents are known from German Offenlegungsschriften 3 319 183 and 3 341 013.
  • the use of succinic acid halamides as corrosion inhibitors in petroleum production and processing is not yet known.
  • the invention relates to salts of alkenylsuccinic acid halamides of the formulas
  • R 1 is C 6 -C 100 , preferably C 9 -C 22 alkenyl
  • A is the protonated residue of an amidamine of the formula II
  • R 2 is C 5 -C 22 -, preferably C 10 -C 18 alkyl, C 5 -C 22 -, preferably g s-wise C 10 -C 18 alkenyl or cycloalkyl
  • R 3 is a group of the formula - (CH2CHO) H
  • Y is hydrogen or methyl
  • n is a number from 0 to 12
  • x is a number from 1 to 3 mean.
  • Cycloalkyl under R 2 preferably means those groups which are derived from the naphthenic acids.
  • the salts of the formulas Ia and Ib are prepared by first reacting an alkenyl succinic anhydride with excess ammonia, giving the ammonium salts.
  • the reaction can be carried out in an inert organic solvent such as petroleum ether or toluene with gaseous ammonia, the ammonium salt crystallizing out; however, the reaction can just as well be carried out with aqueous ammonia, the ammonium salt being obtained in the form of an aqueous solution.
  • the salts according to the invention are then prepared from these alkenylsuccinic acid half-amide ammonium salts by heating in aqueous solution at about 100 ° C. with an amidamine of the formula II, ammonia escaping.
  • the amidamines are prepared by amidation at about 150 to 160 ° C. of carboxylic acids with amines such as diethylene triamine, triethylene tetramine or tetraethylene pentamine and optionally subsequent oxyalkylation with ethylene oxide or propylene oxide under customarily known reaction conditions.
  • solutions of the compounds according to the invention obtained in the synthesis can be used directly without isolation of the end product.
  • These solutions are expediently diluted with a suitable solvent, for example with a low alcohol, and adjusted to a concentration of about 30 to 50% of active substance.
  • a good corrosion protection effect is obtained by adding this commercial product in quantities of 5 to 100, preferably 10 to 50 ppm to the petroleum or petroleum products.
  • a dynamic test (so-called "wheel test”) was used to test the inhibitor compositions, a method by which the corrosion inhibitors for oil and gas production are tested.
  • Kerosene which contained salt water with 5% by weight NaCl, based on water, was used as the test medium.
  • the emulsion contained 90% by weight of salt water and was saturated with H 2 S or CO 2 .
  • the degreased and weighed sheets were then introduced into the emulsions and subjected to mechanical movement (40 rpm by means of a shaft rotating the test vessels) at 70 ° C. for 24 hours.
  • test sheet strips were then cleaned with an inhibiting acid, degreased and weighed after drying to determine the weight loss.

Abstract

Salze von Alkenylbernsteinsäurehalbamiden der Formeln <IMAGE> wobei R¹ C6-C22-, vorzugsweise C9-C18-Alkenyl, A den protonierten Rest eines Amidamins der Formel II <IMAGE> R²C5-C22-, vorzugsweise C10-C18-Alkyl, C5-C22-, vorzugsweise C10-C18-Alkenyl oder Cycloalkyl, R³ eine Gruppe der Formel - (CH2?HO)nH, R<4> entweder eine Gruppe der Formel -COR² und gleichzeitig R<5> Wasserstoff oder R<4> und R<5> gleichzeitig die gleiche Bedeutung wie R³ haben, Y Wasserstoff oder Methyl, n eine Zahl von 0 bis 12 und x eine Zahl von 1 bis 3 bedeuten. Diese Verbindungen eignen sich als Korrosionsinhibitoren bei Wasser-in-Öl-Emulsionen, insbesondere bei Erdöl und Erdölprodukten.Salts of alkenylsuccinic acid halamides of the formulas <IMAGE> where R¹ is C6-C22-, preferably C9-C18-alkenyl, A is the protonated residue of an amidamine of the formula II <IMAGE> R²C5-C22-, preferably C10-C18-alkyl, C5-C22- , preferably C10-C18-alkenyl or cycloalkyl, R³ is a group of the formula - (CH2? HO) nH, R <4> is either a group of the formula -COR² and at the same time R <5> is hydrogen or R <4> and R <5 > have the same meaning as R³, Y is hydrogen or methyl, n is a number from 0 to 12 and x is a number from 1 to 3. These compounds are suitable as corrosion inhibitors in water-in-oil emulsions, in particular in petroleum and petroleum products.

Description

Das Problem der Korrosion stellt sich bei allen Prozessen der Erdölgewinnung und -Verarbeitung, bei denen Eisen oder Eisen enthaltende Metalle mit wäßrigen Systemen in Berührung kommen. Besonders gravierend sind die Probleme bei der Einwirkung von Salzwasser, Kohlensäure- und Schwefelwasserstoff. Als Korrosionsinhibitoren werden meist Amine oder quaternäre Ammoniumverbindungen eingesetzt. Die Schutzwirkung der bekannten Handelsprodukte ist aber häufig unzureichend oder verschlechtert sich nach kurzer Zeit, da sich die Zusammensetzung von frisch gefördertem Rohöl laufend ändert. Insbesondere nehmen die korrosiven Bestandteile im Verlauf einer Förderung zu, wenn z.B. zur Erhöhung der Feldausbeute mit Salzwasser geflutet wird. Es besteht daher weltweit ein Bedarf nach neuen, besser wirkenden Korrosionsschutzmitteln und es werden immer höhere Anforderungen gestellt.The problem of corrosion arises in all processes of oil production and processing in which metals containing iron or iron come into contact with aqueous systems. The problems associated with exposure to salt water, carbonic acid and hydrogen sulfide are particularly serious. Amines or quaternary ammonium compounds are mostly used as corrosion inhibitors. However, the protective effect of the known commercial products is often inadequate or deteriorates after a short time, since the composition of freshly extracted crude oil is constantly changing. In particular, the corrosive components increase in the course of funding, e.g. is flooded with salt water to increase the field yield. There is therefore a need worldwide for new, better-acting anti-corrosion agents and the demands are increasing.

Es wurde nun gefunden, daß durch Verwendung der im folgenden beschriebenen Amidamin-Salze von Alkenylbernsteinsäurehalbamiden eine ausgezeichnete Korrosionsschutzwirkung für Wasser-in-Öl-Emulsionen, wie sie beim Erdöl vorliegen, erzielt werden kann. It has now been found that by using the amidamine salts of alkenylsuccinic acid halamides described below, an excellent corrosion protection effect for water-in-oil emulsions, such as are present in petroleum, can be achieved.

Verschiedene Bernsteinsäurederivate sind schon als Korrosionsschutzmittel bekannt. So werden z.B. Alkyl- oder Alkenylbernsteinsäure-halbester im US Patent 4 053 426 beschrieben, die in Form der Aminsalze für Schmiermittel und wäßrige Metallbearbeitungsflüssigkeiten eingesetzt werden. Das US Patent 4 235 874 beschreibt Alkenylbernsteinsäure oder -anhydrid und Triester von Triethanolamin als Korrosionsinhibitoren für raffinierte Erdöl-Produkte. Für die gleichen Anwendungsgebiete werden im US Patent 4 148 605 Ester-dicarbonsäuren beschrieben, die durch Umsetzung von Alkenylbernsteinsäureanhydrid mit Hydroxy-carbonsäuren erhalten werden.Various succinic acid derivatives are already known as anti-corrosion agents. For example, alkyl or alkenylsuccinic acid half esters are described in US Pat. No. 4,053,426, which are used in the form of the amine salts for lubricants and aqueous metalworking fluids. US Patent 4,235,874 describes alkenyl succinic acid or anhydride and triesters of triethanolamine as corrosion inhibitors for refined petroleum products. For the same fields of application, US Pat. No. 4,148,605 Ester dicarboxylic acids described, which are obtained by reacting alkenyl succinic anhydride with hydroxy carboxylic acids.

Bekannt sind auch bestimmte Bernsteinsäure-halbamide: So werden in der US Patentschrift 2 490 744 Umsetzungsprodukte von Alkenylbernsteinsäureanhydriden mit primären Aminen im Mol-Verhältnis 1,25 bis 2:1 als Rostschutzmittel in Schmierölen genannt, wobei die Gesamtzahl der Kohlenstoffatome im Reaktionsprodukt zwischen 28 und 50 liegen soll.Certain succinic acid half-amides are also known: for example, US Pat. No. 2,490,744 lists reaction products of alkenylsuccinic anhydrides with primary amines in a molar ratio of 1.25 to 2: 1 as rust inhibitors in lubricating oils, the total number of carbon atoms in the reaction product being between 28 and 50 should be.

Darüber hinaus werden in der deutschen Offenlegungsschrift 3 300 874 Alkanolaminsalze von Alkenylbernsteinsäure-halbamiden als Korrosionsschutzmittel für wäßrige Systeme beschrieben; diese Verbindungen werden hergestellt durch Umsetzung von Alkenylbernsteinsäureanhydriden mit primären CI-Cl0-Aminen und anschließende Neutralisation mit C2-C4-Alkanolaminen. Weitere Alkenylbernsteinsäurehalbamide und deren Verwendung als Korrosionsschutzmittel sind aus den deutschen Offenlegungsschriften 3 319 183 und 3 341 013 bekannt. Die Verwendung von Bernsteinsäurehalbamiden als Korrosionsinhibitoren bei der Erdölgewinnung und -verarbeitung ist bisher nicht bekannt.In addition, the German Offenlegungsschrift 3,300,874 alkanolamine salts of alkenylsuccinic acid half-amides are described as corrosion inhibitors for aqueous systems; these compounds are prepared by reacting alkenylsuccinic anhydrides with primary CI - Cl0 amines and subsequent neutralization with C 2 -C 4 alkanolamines. Further alkenylsuccinic acid halamides and their use as corrosion protection agents are known from German Offenlegungsschriften 3 319 183 and 3 341 013. The use of succinic acid halamides as corrosion inhibitors in petroleum production and processing is not yet known.

Gegenstand der Erfindung sind Salze von Alkenylbernsteinsäurehalbamiden der FormelnThe invention relates to salts of alkenylsuccinic acid halamides of the formulas

Figure imgb0001
wobei R1 C6-C100-, vorzugsweise C9-C22-Alkenyl, A den protonierten Rest eines Amidamins der Formel II
Figure imgb0002
R2 C5-C22-, vorzugsweise C10-C18-Alkyl, C5-C22-, vorzugs-weise C10-C18-Alkenyl oder Cycloalkyl, R3 eine Gruppe der Formel -(CH2CHO) H, R entweder eine Gruppe der Formel Y -COR2 und gleichzeitig R5 Wasserstoff oder R und R5 gleichzeitig die gleiche Bedeutung wie R3 haben, Y Wasserstoff oder Methyl, n eine Zahl von 0 bis 12 und x eine Zahl von 1 bis 3 bedeuten. Cycloalkyl unter R2 bedeutet vorzugsweise solche Gruppen, die sich von den Naphthensäuren herleiten.
Figure imgb0001
 where R 1 is C 6 -C 100 , preferably C 9 -C 22 alkenyl, A is the protonated residue of an amidamine of the formula II
Figure imgb0002
 R 2 is C 5 -C 22 -, preferably C 10 -C 18 alkyl, C 5 -C 22 -, preferably g s-wise C 10 -C 18 alkenyl or cycloalkyl, R 3 is a group of the formula - (CH2CHO) H, R either a group of the formula Y -COR 2 and simultaneously R 5 is hydrogen or R and R 5 have the same meaning as R 3 , Y is hydrogen or methyl, n is a number from 0 to 12 and x is a number from 1 to 3 mean. Cycloalkyl under R 2 preferably means those groups which are derived from the naphthenic acids.

Die Herstellung der Salze der Formel Ia und Ib erfolgt in der Weise, daß zunächst ein Alkenylbernsteinsäureanhydrid mit überschüssigem Ammoniak umgesetzt wird, wobei man die Ammoniumsalze erhält. Die Umsetzung kann in einem inerten organischen Lösungsmittel wie Petrolether oder Toluol mit gasförmigem Ammoniak erfolgen, wobei das Ammoniumsalz auskristallisiert; die Reaktion kann aber ebensogut mit wäßrigem Ammoniak durchgeführt werden, wobei das Ammoniumsalz in Form einer wäßrigen Lösung anfällt.The salts of the formulas Ia and Ib are prepared by first reacting an alkenyl succinic anhydride with excess ammonia, giving the ammonium salts. The reaction can be carried out in an inert organic solvent such as petroleum ether or toluene with gaseous ammonia, the ammonium salt crystallizing out; however, the reaction can just as well be carried out with aqueous ammonia, the ammonium salt being obtained in the form of an aqueous solution.

Aus diesen Alkenylbernsteinsäure-halbamid-Ammoniumsalzen werden dann die erfindungsgemäßen Salze hergestellt durch Erhitzen in wäßriger Lösung bei ca. 100°C mit einem Amidamin der Formel II, wobei Ammoniak entweicht. Die Amidamine werden hergestellt durch Amidierung bei ca. 150 bis 160°C von Carbonsäuren mit Aminen wie Diethylentriamin, Triethylentetramin oder Tetraethylenpentamin und gegebenenfalls anschließender Oxalkylierung mit Ethylenoxid oder Propylenoxid unter üblicherweise bekannten Reaktionsbedingungen.The salts according to the invention are then prepared from these alkenylsuccinic acid half-amide ammonium salts by heating in aqueous solution at about 100 ° C. with an amidamine of the formula II, ammonia escaping. The amidamines are prepared by amidation at about 150 to 160 ° C. of carboxylic acids with amines such as diethylene triamine, triethylene tetramine or tetraethylene pentamine and optionally subsequent oxyalkylation with ethylene oxide or propylene oxide under customarily known reaction conditions.

Die bei der Synthese erhaltenen Lösungen der erfindungsgemäßen Verbindungen können ohne Isolierung des Endprodukts direkt weiterverwendet werden. Zweckmäßigerweise verdünnt man diese Lösungen mit einem geeigneten Lösemittel, beispielsweise mit einem niedrigen Alkohol und stellt auf eine Konzentration von ca. 30 bis 50 % an Wirksubstanz ein. Durch Zugabe dieser Handelsware in Mengen von 5 bis 100, vorzugsweise 10 bis 50 ppm zum Erdöl oder Erdölprodukten erhält man eine gute Korrosionsschutzwirkung.The solutions of the compounds according to the invention obtained in the synthesis can be used directly without isolation of the end product. These solutions are expediently diluted with a suitable solvent, for example with a low alcohol, and adjusted to a concentration of about 30 to 50% of active substance. A good corrosion protection effect is obtained by adding this commercial product in quantities of 5 to 100, preferably 10 to 50 ppm to the petroleum or petroleum products.

Allgemeine Arbeitsvorschrift für die Beispiele 1 - 4:General working instructions for Examples 1 - 4:

In einem Reaktionsgefäß legt man 2 Mol Ammoniak in Form einer ca. 25%igen wäßrigen Lösung vor. Unter Rühren tropft man dann 1 Mol eines Alkenylbernsteinsäureanhydrids langsam zu, wobei die Innentemperatur durch Kühlen bei 0 - 5'C gehalten wird. Dann rührt man noch 2 Stunden bei Raumtemperatur, worauf 1 Mol eines Amidamins (Formel II) zugesetzt werden. Die Temperatur wird dann auf 100°C erhöht, wobei Ammoniak entweicht und Wasser abdestilliert wird. Nach 2 Stunden läßt man erkalten und setzt das gewünschte Lösungsmittel (z.B. Isobutanol oder Methanol) zu und füllt ab.2 moles of ammonia are placed in the form of an approximately 25% aqueous solution in a reaction vessel. 1 mol of an alkenylsuccinic anhydride is then slowly added dropwise with stirring, the internal temperature being kept at 0-5'C by cooling. The mixture is then stirred for a further 2 hours at room temperature, whereupon 1 mol of an amidamine (formula II) is added. The temperature is then raised to 100 ° C., ammonia escaping and water being distilled off. After 2 hours, the mixture is allowed to cool, the desired solvent (e.g. isobutanol or methanol) is added and the product is filled off.

Beispiel 1example 1

Nach der allgemeinen Arbeitsvorschrift setzt man zunächst 136 g (2 Mol) Ammoniak 25%ig mit 224 g (1 Mol) Tripropenylbernsteinsäureanhydrid um. Dann setzt man 607 g (1 Mol) des Amidamins II1 (hergestellt aus 2 Mol Talgfettsäure und 1 Mol Diethylentriamin) zu

Figure imgb0003
R = Alkylkette der Talgfettsäure und verfährt weiter wie in der allgemeinen Vorschrift beschrieben. Nach Reaktionsende werden 848 g Isobutanol zugesetzt und man erhält eine gelbe Lösung mit einem Wirkstoffgehalt von 50 %.According to the general working procedure, 136 g (2 mol) 25% ammonia are first reacted with 224 g (1 mol) tripropenylsuccinic anhydride. Then 607 g (1 mol) of amidamine II 1 (prepared from 2 mol of tallow fatty acid and 1 mol of diethylene triamine) are added
Figure imgb0003
 R = alkyl chain of tallow fatty acid and continues as described in the general regulation. After the end of the reaction, 848 g of isobutanol are added and a yellow solution with an active substance content of 50% is obtained.

Beispiel 2Example 2

Nach der allgemeinen Arbeitsvorschrift setzt man 136 g (2 Mol) Ammoniak (25 %) mit 266 g (1 Mol) Tetrapropenylbernsteinsäureanhydrid um. Dazu gibt man 780 g (1 Mol) Amidamin II2 (hergestellt aus 2 mol Naphthensäure, 1 Mol Diethylentriamin und 3 Mol Ethylenoxid)

Figure imgb0004
R = Alkylgerüst der Naphthensäure und verfährt weiter wie in der allgemeinen Vorschrift beschrieben. Zum Schluß setzt man 1060 g Methanol zu, worauf man eine braune Lösung enthält, die die Wirksubstanz zu 50 % enthält.According to the general procedure, 136 g (2 mol) of ammonia (25%) are reacted with 266 g (1 mol) of tetrapropenyl succinic anhydride. 780 g (1 mol) of amidamine II 2 (prepared from 2 mol of naphthenic acid, 1 mol of diethylene triamine and 3 mol of ethylene oxide) are added
Figure imgb0004
 R = alkyl skeleton of naphthenic acid and proceeds as described in the general instructions. Finally, 1060 g of methanol are added, whereupon one contains a brown solution which contains 50% of the active substance.

Beispiel 3Example 3

Nach der allgemeinen Arbeitsvorschrift setzt man zunächst 136 g (2 Mol) Ammoniak (25 % wäßrig) mit 224 g (1 Mol) mripropenylbernsteinsäureanhydrid um. Dann gibt man 1020 g (1 Mol) Amidamin II3 (hergestellt aus 2 Mol Tallölfettsäure, 1 Mol Triethylentetramin und 6 Mol Propylenoxid) zu

Figure imgb0005
R = Alkylkette der Tallölfettsäure x+y = 6 und verfährt weiter wie in der allgemeinen Vorschrift beschrieben. Nach Zusatz von 1255 g Methanol erhält man eine braune Lösung mit einem Wirkstoffgehalt von 50According to the general procedure, 136 g (2 mol) of ammonia (25% aqueous) are first reacted with 224 g (1 mol) of mripropenylsuccinic anhydride. Then 1020 g (1 mol) of amidamine II 3 (prepared from 2 mol of tall oil fatty acid, 1 mol of triethylene tetramine and 6 mol of propylene oxide) are added
Figure imgb0005
 R = alkyl chain of tall oil fatty acid x + y = 6 and continues as described in the general regulation. After adding 1255 g of methanol, a brown solution with an active substance content of 50 is obtained

Beispiel 4Example 4

Nach der allgemeinen Arbeitsvorschrift setzt man 136 g (2 Mol) Ammoniak (25 % wäßrig) zunächst mit 350 g (1 Mol) Octadecenylbernsteinsäureanhydrid um. Dann setzt man 1250 g (1 Mol) Amidamin 114 (hergestellt aus 2 Mol Talgfettsäure, 1 Mol Tetraethylenpentamin und 12 Mol Ethylenoxid) zu

Figure imgb0006
R = Alkylkette der Talgfettsäure x+y+z = 12 und verfährt weiter wie in der allgemeinen Vorschrift beschrieben. Nach Zugabe von 1600 g Isobutanol erhält man eine braune Lösung, die die Wirksubstanz zu 50 % enthält.According to the general procedure, 136 g (2 mol) of ammonia (25% aqueous) are first reacted with 350 g (1 mol) of octadecenylsuccinic anhydride. Then 1250 g (1 mol) of amidamine 11 4 (prepared from 2 mol of tallow fatty acid, 1 mol of tetraethylene pentamine and 12 mol of ethylene oxide) are added
Figure imgb0006
 R = alkyl chain of tallow fatty acid x + y + z = 12 and proceeds as described in the general instructions. After adding 1600 g of isobutanol, a brown solution is obtained which contains 50% of the active substance.

Beispiel 5Example 5

Nach der allgemeinen Arbeitsvorschrift setzt man zunächst 136 g (2 Mol) Ammoniak (25%ig) mit 224 g (1 Mol) Tripropenylbernsteinsäureanhydrid um. Dann setzt man 385 g (1 Mol) des Amidamins II5 (hergestellt aus 1 Mol Naphthensäure und 1 Mol Diethylentriamin) zu

Figure imgb0007
R = Alkylgerüst der Naphthensäure und verfährt weiter wie in der allgemeinen Vorschrift beschrieben. Nach Reaktionsende werden 625 g Toluol zugesetzt und man erhält eine braune Lösung mit einem Wirkstoffgehalt von 50 %.According to the general procedure, 136 g (2 mol) of ammonia (25%) are first reacted with 224 g (1 mol) of tripropenylsuccinic anhydride. Then 385 g (1 mol) of amidamine II 5 (prepared from 1 mol of naphthenic acid and 1 mol of diethylene triamine) are added
Figure imgb0007
 R = alkyl skeleton of naphthenic acid and proceeds as described in the general instructions. After the end of the reaction, 625 g of toluene are added and a brown solution with an active substance content of 50% is obtained.

Die nachfolgend beschriebene Ausprüfung zeigt die hervorragenden Korrosionsschutzeigenschaften dieser Verbindungsklasse. Zum Vergleich wurden die Handelsprodukte Visco 938 und Servo CK 378 mitgeprüft.The test described below shows the excellent corrosion protection properties of this connection class. For comparison, the commercial products Visco 938 and Servo CK 378 were also tested.

Zur Prüfung der Inhibitorkompositionen wurde ein dynamischer Test (sog. "Wheel-Test") herangezogen, eine Methode, womit die Korrosionsinhibitoren für die Erdöl- und Erdgasförderung getested werden.A dynamic test (so-called "wheel test") was used to test the inhibitor compositions, a method by which the corrosion inhibitors for oil and gas production are tested.

Als Testcoupons wurden Stahlbleche der Abmessungen 130 mm x 10 mm x 1 mm gewählt. Diese Blechstreifen wurden geschmirgelt, mit Toluol entfettet und gewogen. Als Testmedium diente Kerosin, das Salzwasser mit 5 Gew.-% NaCl - bezogen auf Wasser - emulgiert enthielt. Die Emulsion enthielt 90 Gew.-% Salzwasser und war mit H2S bzw. C02 gesättigt.Steel sheets measuring 130 mm x 10 mm x 1 mm were chosen as test coupons. These strips of metal were sanded, degreased with toluene and weighed. Kerosene, which contained salt water with 5% by weight NaCl, based on water, was used as the test medium. The emulsion contained 90% by weight of salt water and was saturated with H 2 S or CO 2 .

Dann wurden 10, 20 und 50 ppm - bezogen auf das Gewicht der Emulsion - an Inhibitor zugesetzt.Then 10, 20 and 50 ppm - based on the weight of the emulsion - of inhibitor were added.

Die entfetteten und gewogenen Bleche wurden anschließend in die Emulsionen eingebracht und bei 70°C 24 Stunden einer mechanischen Bewegung (40 Upm mittels einer die Testgefäße drehenden Welle) unterzogen.The degreased and weighed sheets were then introduced into the emulsions and subjected to mechanical movement (40 rpm by means of a shaft rotating the test vessels) at 70 ° C. for 24 hours.

Die Testblechstreifen wurden anschließend mit einer inhibierenden Säure gereinigt, entfettet und nach Trocknung zur Bestimmung des Gewichtsverlustes gewogen. Die Korrosionsraten sind in mpy (mills per year) angegeben (39.4 mpy = 1 mm/Jahr). Zum Vergleich wurde der Blindwert (Versuch ohne Inhibitorzusatz) ermittelt.The test sheet strips were then cleaned with an inhibiting acid, degreased and weighed after drying to determine the weight loss. The corrosion rates are given in mpy (mills per year) (39.4 mpy = 1 mm / year). For comparison, the blank value (test without addition of inhibitor) was determined.

Die mit dieser Testmethode erhaltenen Ergebnisse sind in der folgenden Tabelle zusammengefaßt.

Figure imgb0008
The results obtained with this test method are summarized in the following table.
Figure imgb0008

Claims (3)

1. Salze von Alkenylbernsteinsäurehalbamiden der Formeln
Figure imgb0009
wobei R1 C6-C22-, vorzugsweise C9-C18-Alkenyl, A den protonierten Rest eines Amidamins der Formel II
Figure imgb0010
R2 C5-C22-, vorzugsweise C10-C18-Alkyl, C5-C22-, vorzugsweise C10-C18-Alkenyl oder Cycloalkyl, R3 eine Gruppe der Formel -(CH2CHO)nH, R4 entweder eine Gruppe Y der Formel -COR2 und gleichzeitig R5 Wasserstoff oder R4 und R5 gleichzeitig die gleiche Bedeutung wie R3 haben, Y Wasserstoff oder Methyl, n eine Zahl von 0 bis 12 und x eine Zahl von 1 bis 3 bedeuten.1. Salts of alkenylsuccinic acid half-amides of the formulas
Figure imgb0009
 wherein R 1 is C 6 -C 22 , preferably C 9 -C 18 alkenyl, A is the protonated residue of an amidamine of the formula II
Figure imgb0010
 R 2 is C 5 -C 22 -, preferably C 10 -C 18 alkyl, C 5 -C 22 -, preferably C 10 -C 18 alkenyl or cycloalkyl, R 3 is a group of the formula - (CH 2 CHO) n H , R 4 either a group Y of the formula -COR 2 and simultaneously R 5 is hydrogen or R 4 and R 5 have the same meaning as R 3 , Y is hydrogen or methyl, n is a number from 0 to 12 and x is a number of 1 to 3 mean. 2. Verfahren zur Herstellung der Verbindungen nach Anspruch 1, dadurch gekennzeichnet, daß man ein Alkenylbernsteinsäureanhydrid der Formel
Figure imgb0011
 mit Ammoniak umsetzt und die dabei erhaltenen Alkenylbernsteinsäure-halbamid-Ammoniumsalze weiter mit einem Amidamin der Formel
Figure imgb0012
umsetzt.2. A process for the preparation of the compounds according to claim 1, characterized in that an alkenyl succinic anhydride of the formula
Figure imgb0011
 reacted with ammonia and the alkenylsuccinic acid-half-amide ammonium salts obtained further with an amidamine of the formula
Figure imgb0012
 implements. 3. Verwendung der Verbindungen nach Anspruch 1 als Korrosionsinhibitoren bei Wasser-in-öl-Emulsionen.3. Use of the compounds according to claim 1 as corrosion inhibitors in water-in-oil emulsions.
EP85116667A 1985-01-16 1985-12-31 Salts of alkenylsuccinamic acids, process for their preparation and their use as corrosion inhibitors Expired EP0191952B1 (en)

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DE19853501180 DE3501180A1 (en) 1985-01-16 1985-01-16 SALTS OF ALKENYLSBERSTALIC ACID HALBAMIDES, METHOD FOR THE PRODUCTION THEREOF AND THEIR USE AS CORROSION INHIBITORS
DE3501180 1985-01-16

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0359048A2 (en) * 1988-09-03 1990-03-21 Hoechst Aktiengesellschaft Amidoamine salts of alkenylsuccinic acid derivatives, method for their preparation and their use as corrosion inhibitors
EP0464473A1 (en) * 1990-06-23 1992-01-08 Hoechst Aktiengesellschaft Alkenylsuccinic monoamide salts and their use as corrosion inhibitors and emulsifiers for metal working oils
FR2700336A1 (en) * 1993-01-11 1994-07-13 Hoechst France Substituted succinimides, process for their preparation and their use as corrosion inhibitors
EP1359208A2 (en) * 2002-04-23 2003-11-05 Rohm And Haas Company Amine-acid reaction products as asphaltene dispersants in crude oil

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5250225A (en) * 1991-02-04 1993-10-05 Basf Aktiengesellschaft Ammonium salt of an alkenylsuccinic half-amide and the use thereof as corrosion inhibitor in oil and/or gas production technology
US20040232042A1 (en) * 2003-05-23 2004-11-25 Ravindranath Mukkamala Amine-acid reaction products as asphaltene dispersants in crude oil

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4332737A (en) * 1980-04-18 1982-06-01 E. I. Du Pont De Nemours And Company Acid reaction products of polymeric amines
DE3300874A1 (en) * 1983-01-13 1984-07-19 Henkel KGaA, 4000 Düsseldorf Succinic acid derivatives as corrosion protection agents
EP0127132A1 (en) * 1983-05-27 1984-12-05 Hoechst Aktiengesellschaft Use of alkenylsuccinic monoamides as corrosion inhibitors

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3341013A1 (en) * 1983-11-12 1985-05-23 Henkel KGaA, 4000 Düsseldorf AMBER ACID MONO-DIALKYLAMIDES AS WATER-SOLUBLE CORROSION PROTECTORS

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4332737A (en) * 1980-04-18 1982-06-01 E. I. Du Pont De Nemours And Company Acid reaction products of polymeric amines
DE3300874A1 (en) * 1983-01-13 1984-07-19 Henkel KGaA, 4000 Düsseldorf Succinic acid derivatives as corrosion protection agents
EP0127132A1 (en) * 1983-05-27 1984-12-05 Hoechst Aktiengesellschaft Use of alkenylsuccinic monoamides as corrosion inhibitors

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0359048A2 (en) * 1988-09-03 1990-03-21 Hoechst Aktiengesellschaft Amidoamine salts of alkenylsuccinic acid derivatives, method for their preparation and their use as corrosion inhibitors
EP0359048A3 (en) * 1988-09-03 1991-10-23 Hoechst Aktiengesellschaft Amidoamine salts of alkenylsuccinic acid derivatives, method for their preparation and their use as corrosion inhibitors
EP0464473A1 (en) * 1990-06-23 1992-01-08 Hoechst Aktiengesellschaft Alkenylsuccinic monoamide salts and their use as corrosion inhibitors and emulsifiers for metal working oils
FR2700336A1 (en) * 1993-01-11 1994-07-13 Hoechst France Substituted succinimides, process for their preparation and their use as corrosion inhibitors
EP0606795A1 (en) * 1993-01-11 1994-07-20 Societe Francaise Hoechst Substituted succinimides, process for their preparation and application as corrosion inhibitors
US5382667A (en) * 1993-01-11 1995-01-17 Societe Francaise Hoechst Substituted succinimides as corrosion inhibitors
EP1359208A2 (en) * 2002-04-23 2003-11-05 Rohm And Haas Company Amine-acid reaction products as asphaltene dispersants in crude oil
EP1359208A3 (en) * 2002-04-23 2004-11-03 Rohm And Haas Company Amine-acid reaction products as asphaltene dispersants in crude oil

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DE3501180A1 (en) 1986-07-17
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JPS61167651A (en) 1986-07-29
US4722812A (en) 1988-02-02

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