EP0002780A1 - Use of corrosion inhibitors in aqueous systems - Google Patents
Use of corrosion inhibitors in aqueous systems Download PDFInfo
- Publication number
- EP0002780A1 EP0002780A1 EP78101757A EP78101757A EP0002780A1 EP 0002780 A1 EP0002780 A1 EP 0002780A1 EP 78101757 A EP78101757 A EP 78101757A EP 78101757 A EP78101757 A EP 78101757A EP 0002780 A1 EP0002780 A1 EP 0002780A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- carbon atoms
- water
- salts
- aqueous systems
- corrosion inhibitors
- 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.)
- Granted
Links
- 238000005260 corrosion Methods 0.000 title claims abstract description 18
- 230000007797 corrosion Effects 0.000 title claims abstract description 17
- 239000003112 inhibitor Substances 0.000 title claims abstract description 4
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 13
- 239000006260 foam Substances 0.000 claims abstract description 12
- 150000003839 salts Chemical class 0.000 claims abstract description 7
- 239000000203 mixture Substances 0.000 claims description 9
- 150000001875 compounds Chemical class 0.000 claims description 5
- 150000002689 maleic acids Chemical class 0.000 claims description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims 1
- 229910052799 carbon Inorganic materials 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 14
- 238000000034 method Methods 0.000 abstract description 9
- 239000003795 chemical substances by application Substances 0.000 abstract description 3
- 238000004140 cleaning Methods 0.000 abstract description 2
- 238000001816 cooling Methods 0.000 abstract description 2
- 150000001408 amides Chemical group 0.000 abstract 1
- FSQQTNAZHBEJLS-UPHRSURJSA-N maleamic acid Chemical compound NC(=O)\C=C/C(O)=O FSQQTNAZHBEJLS-UPHRSURJSA-N 0.000 abstract 1
- 150000002688 maleic acid derivatives Chemical class 0.000 abstract 1
- 238000012360 testing method Methods 0.000 description 11
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 8
- -1 amine salts Chemical class 0.000 description 8
- 239000007788 liquid Substances 0.000 description 8
- 239000011976 maleic acid Substances 0.000 description 8
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 8
- 239000002253 acid Substances 0.000 description 7
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 7
- 229910001060 Gray iron Inorganic materials 0.000 description 6
- 150000001412 amines Chemical class 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical class OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 6
- 235000002639 sodium chloride Nutrition 0.000 description 6
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 5
- 239000007795 chemical reaction product Substances 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 238000005187 foaming Methods 0.000 description 4
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 4
- 239000012299 nitrogen atmosphere Substances 0.000 description 4
- DZDVMKLYUKZMKK-UHFFFAOYSA-N 7-methyloctan-1-amine Chemical class CC(C)CCCCCCN DZDVMKLYUKZMKK-UHFFFAOYSA-N 0.000 description 3
- 150000007513 acids Chemical class 0.000 description 3
- 239000005068 cooling lubricant Substances 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- PWBYEVGYPCMAKF-UHFFFAOYSA-N 10-methylundecan-1-amine Chemical class CC(C)CCCCCCCCCN PWBYEVGYPCMAKF-UHFFFAOYSA-N 0.000 description 2
- LPULCTXGGDJCTO-UHFFFAOYSA-N 6-methylheptan-1-amine Chemical class CC(C)CCCCCN LPULCTXGGDJCTO-UHFFFAOYSA-N 0.000 description 2
- 229910001208 Crucible steel Inorganic materials 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000000498 cooling water Substances 0.000 description 2
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 2
- 239000000839 emulsion Substances 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 238000005555 metalworking Methods 0.000 description 2
- 238000006386 neutralization reaction Methods 0.000 description 2
- 239000011814 protection agent Substances 0.000 description 2
- 230000035945 sensitivity Effects 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid Chemical compound OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 2
- FALRKNHUBBKYCC-UHFFFAOYSA-N 2-(chloromethyl)pyridine-3-carbonitrile Chemical compound ClCC1=NC=CC=C1C#N FALRKNHUBBKYCC-UHFFFAOYSA-N 0.000 description 1
- LTHNHFOGQMKPOV-UHFFFAOYSA-N 2-ethylhexan-1-amine Chemical compound CCCCC(CC)CN LTHNHFOGQMKPOV-UHFFFAOYSA-N 0.000 description 1
- LJQFHDUFUVMPSP-UHFFFAOYSA-N 8-methylnonan-1-amine Chemical class CC(C)CCCCCCCN LJQFHDUFUVMPSP-UHFFFAOYSA-N 0.000 description 1
- HDJMDEWQBCBLBY-UHFFFAOYSA-N 9-methyldecan-1-amine Chemical class CC(C)CCCCCCCCN HDJMDEWQBCBLBY-UHFFFAOYSA-N 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- 229910000975 Carbon steel Inorganic materials 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- SLINHMUFWFWBMU-UHFFFAOYSA-N Triisopropanolamine Chemical compound CC(O)CN(CC(C)O)CC(C)O SLINHMUFWFWBMU-UHFFFAOYSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 150000003973 alkyl amines Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 239000012736 aqueous medium Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 239000010962 carbon steel Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000013016 damping Methods 0.000 description 1
- LVTYICIALWPMFW-UHFFFAOYSA-N diisopropanolamine Chemical compound CC(O)CNCC(C)O LVTYICIALWPMFW-UHFFFAOYSA-N 0.000 description 1
- 239000003651 drinking water Substances 0.000 description 1
- 235000020188 drinking water Nutrition 0.000 description 1
- 229910001651 emery Inorganic materials 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000002816 fuel additive Substances 0.000 description 1
- 238000006317 isomerization reaction Methods 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000002609 medium Substances 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000001384 succinic acid Substances 0.000 description 1
- 229940014800 succinic anhydride Drugs 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000008399 tap water Substances 0.000 description 1
- 235000020679 tap water Nutrition 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
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
- the invention relates to the use of alkanolamine salts of maleic acid as low-foaming corrosion inhibitors for metals in aqueous systems.
- DE-AS 11 49 843 discloses amine salts of amic acids which are obtained as lubricants by reacting succinic or maleic anhydride with primary alkylamines which contain 4 to 30 C atoms in the alkyl chain and then neutralizing with such amines. and fuel additives with rust protection.
- the agents mentioned by way of example in this literature reference are oil-soluble and in most cases not water-soluble. Insofar as they are water-soluble, it has been found that they either develop much too strong foam in the above-mentioned systems (see also the mention of the addition of foam absorbers in this patent specification) or they lose a large part of their anticorrosive action with less foam action.
- water solubility and water hardness insensitivity are influenced by the chain length.
- maleic acid isooctyl, isononyl, isodecyl, isoundecyl and / or isododecylamic acids which have been neutralized with mono-, di- or tri-C 2 -C 3 -alkanolamines or mixtures thereof.
- nC 8 and lower such as n-C7 and C 7 isoalkylamines as starting products, greatly weaken the anticorrosive effect of the end products and that end products with starting from a longest chain of isoalkylamines of more than 8 C atoms excessive foaming effect.
- isoalkylamines with more than 7 carbon atoms have a low sensitivity to water hardness as a starting product. Above about 12 carbon atoms, the water hardness sensitivity of the end products is increased very strongly, and the water solubility is also severely restricted.
- Starting compounds for the preparation of the compounds to be used according to the invention are maleic anhydride and primary isoalkylamines having 8 to 12 carbon atoms and having a longest chain of 6 to 8 carbon atoms, such as isooctylamines, isononylamines, isodecylamines, isoundecylamines and isododecylamines, of which the isooctylamines and isononylamines are preferred.
- These amines can also be used in a mixture with corresponding amounts of n-alkylamine. Such mixtures originate e.g. of oxo synthesis.
- the reaction of the maleic anhydride with the amine or amine mixture in question can be carried out by known methods.
- the amic acids obtained are then neutralized with one of the alkanolamines as defined or with mixtures thereof in a manner known per se.
- An excess of alkanolamine is preferably used.
- Special alkanolamines for the purposes of the invention are, for example, di- or triethanolamine or di- and triisopropanolamine or mixtures thereof.
- the most effective products have been found to be the 2-ethylhexyl half-amides and the isononyl half-amides of maleic acid, which have been neutralized with triethanolamine and diethanolamine.
- the results according to the invention are also achieved, as mentioned, if up to 90% by weight of compounds of the formula according to the definition are added to the half-amides, in which R denotes an n-alkyl radical having 8 to 12 carbon atoms.
- R denotes an n-alkyl radical having 8 to 12 carbon atoms.
- the n-octyl-, nonyl-, decyl- and -dodecyl half-amides should be mentioned here in particular.
- the maleic acids formed are mixed with the corresponding alkanolamine in molar ratios of 1: 1 to 2: 8 and stirred until a clear liquid is obtained.
- a crystalline substance is formed with a melting point of 69 ° C and an acid number of 252 (theoretically: 247).
- this maleic acid 30 parts by weight of this maleic acid are then mixed with 70 parts by weight of triethanolamine with a portion of diethanolamine and stirred without additional heating until a clear liquid is obtained.
- a crystalline substance is formed with a melting point of 62 ° C and an acid number of 235 (theoretically: 233).
- a liquid with an acid number of 191 (theoretically: 191) is formed.
- the corrosion protection effect was determined by the so-called “Herberts” corrosion test and the “gray cast iron” filter test.
- the foam damping was determined by the "IG impact method” based on DIN 53 902.
- the corrosion protection effect is illustrated in 1% aqueous solution of active substance and at a water hardness of 10 0 dH using the Herberts test system introduced in the metalworking sector.
- This consists of a standardized gray cast iron plate and also standardized steel chips of 5 mm length, which are supplied by Alfred Herberts, Coventry / England.
- the square plate with the dimensions 100 x 100 x 5 mm is carefully sanded using a belt grinder with 120 grain and emery belt, washed with white spirit and ethanol and dried with a clean cloth.
- the steel chips supplied with the test system which are obtained under standardized conditions from 0.40% carbon steel, are placed on the prepared cast steel plate in four piles using a suitable metal or plastic spoon with the capacity of a normal teaspoon so that they separate from each other and have the same distance from the edges of the plate.
- the chips should lie in a single layer in the narrowest possible position.
- the solutions or emulsions to be tested for their corrosion behavior are applied to the piles of chips by means of a measuring pipette in such a quantity that the liquid reaching the cast steel plate comes straight from the Chips are held together. After standing for 24 hours in an atmosphere of 70% relative humidity, the chips are shaken off the plate by tilting. The clearly visible outline of the dried aqueous medium remains. Depending on the corrosiveness of the liquid, rust marks of smaller or larger dimensions have formed at the contact points of the chips, which can also have grown together to form a closed rust layer. The assessment can be made by visually estimating the percentage of rust in the area.
- a further corrosion test consists in the gray cast iron filter sample.
- a petri dish with an inner diameter of approx. 10 cm is used with a suitable lid dish.
- a black band round filter is placed in the Petri dish.
- a suitable spoon is used to distribute 5 to 10 g of coarse gray cast iron GG-20 chips onto the filter in such a way that a uniform heap is formed in the middle, which is around 1.5 cm away from the edge.
- the chips have a length of approx. 5 to 8 mm and must be obtained from clean gray cast iron GG-20 material without the use of boron oil or other cooling lubricants. All fine components must be screened.
- the impact method was used based on DIN 53 902.
- the simple test procedure was sufficient, in which the punch with the perforated plate was manually carried out and removed 30 times in 30 s and then carefully pulled out (IG impact method).
- the foam volume is read on the graduated foam cylinder after 1, 5 and 10 min in ml. Information about temperature, concentration and water hardness are also important.
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Lubricants (AREA)
Abstract
Verwendung von Maleinamidsäure-alkanolaminsalzen als Korrosionsschutzmittel in wäßrigen Systemen, d.h. in Reinigungs- und Kühlprozessen, die sich in Gegenwart von Wasser abspielen. Es handelt sich um Maleinamidsäuresalze, die am Amidrest eine C8- bis C12-Isoalkylgruppe, die 6 bis 8 C-Atome in der längsten Kette besitzt, tragen. Die Salze leiten sich von Mono-, Di- oder Trialkanolaminen mit 2 bis 3 C-Atomen pro Alkanolgruppe ab. Diese Mittel sind bei großer Schaumarmut ausgezeichnete Korrosionsschutzmittel - ein Zusatz spezieller Schaumdämpfer ist nicht mehr erforderlich.Use of maleamic acid alkanolamine salts as corrosion inhibitors in aqueous systems, i.e. in cleaning and cooling processes that take place in the presence of water. These are maleic acid salts which carry a C8 to C12 isoalkyl group on the amide residue which has 6 to 8 C atoms in the longest chain. The salts are derived from mono-, di- or trialkanolamines with 2 to 3 carbon atoms per alkanol group. These agents are excellent anti-corrosion agents when there is little foam - it is no longer necessary to add special foam dampers.
Description
Die Erfindung betrifft die Verwendung von AlkanolaminSalzen von Maleinamidsäuren als schaumarme Korrosionsinhibitoren für Metalle in wäßrigen Systemen.The invention relates to the use of alkanolamine salts of maleic acid as low-foaming corrosion inhibitors for metals in aqueous systems.
In technischen Reinigungs- und Kühlprozessen, die sich in Gegenwart von Wasser abspielen, stelle sich immer das Problem des Korrosionsschutzes, wenn korrosionsgefährdete Metalle, vornehmlich Eisen oder eisenhaltige Legierungen, durch diese Prozesse direkt tangiert werden (z.B. wäßrige technische Reiniger, Kühlwässer, Kühlschmierstoffe für die Metallbearbeitung).In technical cleaning and cooling processes that take place in the presence of water, the problem of corrosion protection always arises when metals at risk of corrosion, primarily iron or iron-containing alloys, are directly affected by these processes (e.g. aqueous technical cleaners, cooling water, cooling lubricants for the Metalworking).
Ein weiteres Problem, das bei solchen Prozessen auftritt, vor allem bei Kühlwässern und Kühlschmierstoffen, ist die zu starke Schaumbildung, die vor allem auftritt, wenn dem Wasser organische Korrosionsschutzmittel, die häufig Tensideigenschaften zeigen, zugesetzt werden. Bisher mußten daher meistens zusammen mit dem organischen Korrosionsschutzmittel noch Schaumdämpfer eingesetzt werden.Another problem that occurs with such processes, especially with cooling water and cooling lubricants, is the excessive foaming, which occurs especially when organic corrosion protection agents, which often have surfactant properties, are added to the water. Up to now, foam dampers have therefore mostly had to be used together with the organic corrosion protection agent.
Das Ziel der Erfindung bestand in der Auffindung solcher Additive in den genannten Systemen, die
- 1. wasserlöslich sind,
- 2. eine gute Korrosionsschutzwirkung zeigen,
- 3. möglichst nicht zum Schäumen neigen und
- 4. soweit wie möglich wasserhärteunempfindlich sind.
- 1. are water soluble,
- 2. show a good corrosion protection effect,
- 3. if possible not tend to foam and
- 4. are insensitive to water hardness as far as possible.
Bekannt sind aus der DE-AS 11 49 843 Aminsalze von Amidsäuren, die man durch Umsetzung von Bernstein- oder Maleinsäureanhydrid mit primären Alkylaminen, die 4 bis 30 C-Atome in der Alkylkette enthalten, und anschließender Neutralisation mit solchen Aminen erhält, als Schmier- und Brennstoffadditive mit Rostschutzwirkung. Die in dieser Literaturstelle beispielhaft genannten Mittel sind aber öl- und in den meisten Fällen nicht wasserlöslich. Soweit sie wasserlöslich sind, wurde festgestellt, daß sie in den obengenannten Systemen entweder viel zu starken Schaum entwickeln (siehe auch die Nennung des Zusatzes von Schaumdämpfern in dieser Patentschrift) oder sie verlieren bei geringerer Schaumwirkung einen großen Teil ihrer antikorrosiven Wirkung.DE-AS 11 49 843 discloses amine salts of amic acids which are obtained as lubricants by reacting succinic or maleic anhydride with primary alkylamines which contain 4 to 30 C atoms in the alkyl chain and then neutralizing with such amines. and fuel additives with rust protection. The agents mentioned by way of example in this literature reference are oil-soluble and in most cases not water-soluble. Insofar as they are water-soluble, it has been found that they either develop much too strong foam in the above-mentioned systems (see also the mention of the addition of foam absorbers in this patent specification) or they lose a large part of their anticorrosive action with less foam action.
Es lag nun nahe, für wäßrige Systeme bei der Neutralisation nicht die in DE-AS 11 49 843 genannten Amine, sondern die in diesem Bereich üblichen Alkanolamine zu verwenden. Dabei stellte sich aber heraus, daß hier, je nach Kettenlänge des Restes R gemäß der im Patentanspruch genannten Formel, entweder (bei langer Kette) ausgesprochen starke Schäumer entstehen, die fast wasserlöslich sind, oder (bei kurzer Kette) die Korrosionsschutzwirkung verloren geht.It was now obvious to use not the amines mentioned in DE-AS 11 49 843 for aqueous systems for neutralization, but the alkanolamines customary in this area. It turned out, however, that depending on the chain length of the radical R according to the formula mentioned in the claim, either (in the case of a long chain) extremely strong foams are formed which are almost water-soluble, or (in the case of a short chain) the corrosion protection effect is lost.
Zusätzlich werden auch die Wasserlöslichkeit und die Wasserhärteunempfindlichkeit durch die Kettenlänge beeinflußt.In addition, water solubility and water hardness insensitivity are influenced by the chain length.
Überraschenderweise wurde nun gefunden, daß für einen bestimmten, sehr engen Bereich der Kettenlänge von R, wenn gleichzeitig ein bestimmter Isomerisierungsgrad von R vorliegt, das Ziel der Erfindung erreicht wird.Surprisingly, it has now been found that for a certain, very narrow range of the chain length of R, when a certain degree of isomerization of R is present, the object of the invention is achieved.
Dieses Ziel erreicht man mit solchen speziellen Salzen von Maleinamidsäuren, wie sie gemäß den Patentansprüchen definiert sind.This goal is achieved with such special salts of maleic acid as defined in the claims.
Es handelt sich um Maleinsäure-isooctyl-, isononyl-, -isodecyl-, isoundecyl- und/oder -isododecylamidsäuren, die mit Mono-, Di- oder Tri-C2- bis C3-alkanolaminen oder deren Gemischen neutralisiert worden sind.It is maleic acid isooctyl, isononyl, isodecyl, isoundecyl and / or isododecylamic acids which have been neutralized with mono-, di- or tri-C 2 -C 3 -alkanolamines or mixtures thereof.
Sie unterscheiden sich von denen in der DE-AS 11 49 847 genannten Salzen nicht nur durch die Verwendung der Alkanolamine zur Salzbildung, sondern auch durch die spezielle, in der genannten Auslegeschrift nicht wörtlich offenbarte Amidsäurekomponente. Die Ausgangsstoffe zu ihrer Herstellung sind dort zwar genannt, jedoch nicht die Endprodukte selbst.They differ from the salts mentioned in DE-AS 11 49 847 not only by the use of the alkanolamines for salt formation, but also by the special amic acid component which is not literally disclosed in the abovementioned specification. The starting materials for their production are mentioned there, but not the end products themselves.
Es hat sich gezeigt, daß bereits n-C8- und niedrigere wie n-C7- und C7-Isoalkylamine als Ausgangsprodukte die antikorrosive Wirkung der Endprodukte stark schwächen und daß ab einer längsten Kette der Isoalkylamine von mehr als 8 C-Atomen als Ausgangsprodukte Endprodukte mit zu starker Schaumwirkung entstehen. Eine geringe Wasserhärteempfindlichkeit besteht bei Endprodukten aus Isoalkylaminen mit mehr als 7 C-Atomen als Ausgangsprodukt. Ab etwa 12 C-Atomen wird die Wasserhärteempfindlichkeit der Endprodukte sehr stark erhöht, und auch die Wasserlöslichkeit wird stark eingeschränkt.It has been shown that nC 8 and lower, such as n-C7 and C 7 isoalkylamines as starting products, greatly weaken the anticorrosive effect of the end products and that end products with starting from a longest chain of isoalkylamines of more than 8 C atoms excessive foaming effect. In the case of end products, isoalkylamines with more than 7 carbon atoms have a low sensitivity to water hardness as a starting product. Above about 12 carbon atoms, the water hardness sensitivity of the end products is increased very strongly, and the water solubility is also severely restricted.
Ausgangsverbindungen zur Herstellung der erfindungsgemäß zu verwendenden Verbindungen sind Maleinsäureanhydrid und primäre Isoalkylamine mit 8 bis 12 C-Atomen und mit einer längsten Kette von 6 bis 8 C-Atomen, wie Isooctylamine, Isononylamine, Isodecylamine, Isoundecylamine und Isododecylamine, von denen die Isooctylamine und Isononylamine bevorzugt sind. Diese Amine können auch in Mischung mit entsprechenden n-Alkylaminanteilen eingesetzt werden. Solche Mischungen entstammen z.B. der Oxosynthese.Starting compounds for the preparation of the compounds to be used according to the invention are maleic anhydride and primary isoalkylamines having 8 to 12 carbon atoms and having a longest chain of 6 to 8 carbon atoms, such as isooctylamines, isononylamines, isodecylamines, isoundecylamines and isododecylamines, of which the isooctylamines and isononylamines are preferred. These amines can also be used in a mixture with corresponding amounts of n-alkylamine. Such mixtures originate e.g. of oxo synthesis.
Die Umsetzung des Maleinsäureanhydrids mit dem betreffenden Amin oder Amingemisch kann nach bekannten Methoden erfolgen. Die erhaltenen Amidsäuren werden dann mit einem der definitionsgemäßen Alkanolamine oder auch mit Mischungen davon in an sich bekannter Weise neutralisiert. Dabei wird vorzugsweise ein Überschuß an Alkanolamin verwendet.The reaction of the maleic anhydride with the amine or amine mixture in question can be carried out by known methods. The amic acids obtained are then neutralized with one of the alkanolamines as defined or with mixtures thereof in a manner known per se. An excess of alkanolamine is preferably used.
Spezielle Alkanolamine im Sinne der Erfindung sind beispielsweise Di- oder Triäthanolamin oder Di- und Triisopropanolamin oder deren Gemische.Special alkanolamines for the purposes of the invention are, for example, di- or triethanolamine or di- and triisopropanolamine or mixtures thereof.
Als wirksamste Produkte haben sich die 2-Äthylhexyl-Halbamide und die Isononyl-Halbamide der Maleinsäure erwiesen, die mit Triäthanolamin und Diäthanolamin neutralisiert worden sind.The most effective products have been found to be the 2-ethylhexyl half-amides and the isononyl half-amides of maleic acid, which have been neutralized with triethanolamine and diethanolamine.
Außer mit den genannten Halbamiden allein erzielt man die erfindungsgemäßen Ergebnisse wie gesagt auch dann, wenn den Halbamiden bis zu 90 Gew.% an Verbindungen der definitionsgemäßen Formel zugesetzt sind, in der R einen n-Alkylrest mit 8 bis 12 C-Atomen bedeutet. Hier sind vor allem die n-Octyl-, nonyl-, decyl- und -dodecylhalbamide zu nennen.In addition to the half-amides mentioned, the results according to the invention are also achieved, as mentioned, if up to 90% by weight of compounds of the formula according to the definition are added to the half-amides, in which R denotes an n-alkyl radical having 8 to 12 carbon atoms. The n-octyl-, nonyl-, decyl- and -dodecyl half-amides should be mentioned here in particular.
Maleinsäureanhydrid wird unter N2-Atmosphäre bei 60 bis 70°C geschmolzen, dann wird unter Rühren das entsprechende Amin im Molverhältnis 1 : 1 bei 60 bis 100°C zugegeben und eine halbe Stunde bis eine Stunde nachgerührt.Maleic anhydride is melted under an N 2 atmosphere at 60 to 70 ° C, then the corresponding amine is added in a molar ratio of 1: 1 at 60 to 100 ° C and stirred for half an hour to an hour.
Zur Neutralisation werden die entstandenen Maleinamidsäuren mit dem entsprechenden Alkanolamin in Molverhältnissen von 1 : 1 bis 2 : 8 miteinander gemischt und gerührt, bis sich eine klare Flüssigkeit ergibt.For neutralization, the maleic acids formed are mixed with the corresponding alkanolamine in molar ratios of 1: 1 to 2: 8 and stirred until a clear liquid is obtained.
147 g (1,5 Mol) Maleinsäureanhydrid werden unter N2-Atmosphäre bei 60 bis 70°C geschmolzen, dann werden unter Rühren 193,5 g (1,5 Mol) 2-Äthylhexylamin langsam bei 60 bis 80°C zugegeben und eine halbe Stunde bei 80°C nachgerührt.147 g (1.5 mol) of maleic anhydride are melted under an N 2 atmosphere at 60 to 70 ° C., then 193.5 g (1.5 mol) of 2-ethylhexylamine are slowly added at 60 to 80 ° C. with stirring and one stirred at 80 ° C for half an hour.
Es entsteht eine kristalline Substanz mit einem Schmelzpunkt von 69°C und einer Säurezahl von 252 (theoretisch: 247).A crystalline substance is formed with a melting point of 69 ° C and an acid number of 252 (theoretically: 247).
30 Gewichtsteile dieser Maleinamidsäure werden dann mit 70 Gewichtsteilen Triäthanolamin mit einem Anteil Diäthanolamin gemischt und ohne zusätzliches Erhitzen gerührt, bis sich eine klare Flüssigkeit ergibt.30 parts by weight of this maleic acid are then mixed with 70 parts by weight of triethanolamine with a portion of diethanolamine and stirred without additional heating until a clear liquid is obtained.
147 g (1,5 Mol) Maleinsäureanhydrid werden unter N2-Atmosphäre bei 60 bis 70°C geschmolzen, dann werden unter Rühren 213 g (1,5 Mol) eines Isononylamins langsam bei 60 bis 100°C zugegeben und eine halbe Stunde bis eine Stunde bei dieser Temperatur nachgerührt.147 g (1.5 mol) of maleic anhydride are melted under an N 2 atmosphere at 60 to 70 ° C., then 213 g (1.5 mol) of an isononylamine are slowly added at 60 to 100 ° C. with stirring and half an hour to stirred for one hour at this temperature.
Es entsteht ein kristalliner Stoff mit einem Schmelzpunkt von 62°C und einer Säurezahl von 235 (theoretisch: 233).A crystalline substance is formed with a melting point of 62 ° C and an acid number of 235 (theoretically: 233).
30 Gewichtsteile der entstandenen Maleinamidsäure werden dann mit 70 Gewichtsteilen Triäthanolamin (wie in Beispiel 1) ohne zusätzliches Erwärmen vermischt und gerührt, bis sich eine klare Flüssigkeit ergibt.30 parts by weight of the resulting maleic acid are then mixed with 70 parts by weight of triethanolamine (as in Example 1) without additional heating and stirred until a clear liquid results.
147 g (1,5 Mol) Maleinsäureanhydrid werden unter N2-Atmosphäre bei 60 bis 70°C geschmolzen, dann werden unter Rühren 273 g (1,5 Mol) Isododecylamin (längste Kette: 6 C-Atome) langsam bei 60 bis 80°C zugegeben und eine Stunde bei 80°C nachgerührt.147 g (1.5 mol) of maleic anhydride are melted under an N2 atmosphere at 60 to 70 ° C., then 273 g (1.5 mol) of isododecylamine (longest chain: 6 carbon atoms) are slowly added at 60 to 80 ° with stirring C added and stirred for one hour at 80 ° C.
Es entsteht eine Flüssigkeit mit einer Säurezahl von 191 (theoretisch: 191).A liquid with an acid number of 191 (theoretically: 191) is formed.
30 Gewichtsteile der entstandenen Maleinamidsäure werden dann mit 70 Gewichtsteilen Triäthanolamin (wie in Beispiel 1) ohne zusätzliches Erhitzen vermischt und gerührt, bis eine Flüssigkeit mit leichter, homogen verteilter Trübung entstanden ist.30 parts by weight of the resulting maleic acid are then mixed with 70 parts by weight of triethanolamine (as in Example 1) without additional heating and stirred until a liquid having a slightly, homogeneously distributed turbidity has formed.
Neben den drei in den Beispielen genannten erfindungsgemäßen Produkten werden in der Tabelle eine Reihe anderer Maleinamidsäuren und eine Bernsteinamidsäure als Vergleich herangezogen, womit der äußerst enge Bereich des Zusammentreffens der verschiedenen anwendungstechnischen Eigenschaften nachgewiesen wird, die das Ziel der Erfindung bilden.In addition to the three products according to the invention mentioned in the examples, a number of other maleic acid and a succinic acid are used in the table as a comparison, thus demonstrating the extremely narrow range of the coincidence of the various application properties which form the object of the invention.
Die korrosionsschützende Wirkung wurde durch den sogenannten "Herberts"-Korrosionstest und den "Grauguß"-Filtertest bestimmt. Die Schaumdämpfung wurde durch die "IG-Schlagmethode" in Anlehnung an DIN 53 902 ermittelt.The corrosion protection effect was determined by the so-called "Herberts" corrosion test and the "gray cast iron" filter test. The foam damping was determined by the "IG impact method" based on DIN 53 902.
Die Korrosionstest wurden wie folgt durchgeführt:The corrosion tests were carried out as follows:
Die Korrosionsschutzwirkung wird in an Wirksubstanz 1 %iger wäßriger Lösung und bei einer Wasserhärte von 100d.H. an dem auf dem Metallverarbeitungssektor eingeführten Herberts-Test-System veranschaulicht. Dieses besteht aus einer standardisierten Grauguß-Platte und ebenfalls standardisierten Stahlspänen von 5 mm Länge, die von der Firma Alfred Herberts, Coventry/England geliefert werden. Die quadratische Platte mit den Abmessungen 100 x 100 x 5 mm wird vor der Prüfung mittels einer Bandschleifmaschine mit Körund-Schmirgelband der Körnung 120 sorgfältig abgeschliffen, mit Testbenzin und Äthanol gewaschen sowie mit einem reinen Tuch getrocknet. Dann werden die mit dem Prüfsystem gelieferten Stahlspäne, die unter standardisierten Bedingungen aus 0,40 %igem Kohlenstoffstahl gewonnen werden, mittels eines geeigneten Metall- oder Plastiklöffels mit dem Fassungsvermögen eines normalen Teelöffels in vier Häufchen so auf die vorbereitete Gußstahlplatte gesetzt, daß sie voneinander und von den Rändern der Platte gleichen Abstand haben. Die Späne sollen in einfacher Schicht bei engstmöglicher Lage liegen.The corrosion protection effect is illustrated in 1% aqueous solution of active substance and at a water hardness of 10 0 dH using the Herberts test system introduced in the metalworking sector. This consists of a standardized gray cast iron plate and also standardized steel chips of 5 mm length, which are supplied by Alfred Herberts, Coventry / England. The square plate with the dimensions 100 x 100 x 5 mm is carefully sanded using a belt grinder with 120 grain and emery belt, washed with white spirit and ethanol and dried with a clean cloth. Then the steel chips supplied with the test system, which are obtained under standardized conditions from 0.40% carbon steel, are placed on the prepared cast steel plate in four piles using a suitable metal or plastic spoon with the capacity of a normal teaspoon so that they separate from each other and have the same distance from the edges of the plate. The chips should lie in a single layer in the narrowest possible position.
Die auf ihr Korrosionsverhalten zu prüfenden Lösungen bzw. Emulsionen werden mittels einer Meßpipette in solcher Menge auf die Späne-Häufchen gegeben, daß die die Gußstahlplatte erreichende Flüssigkeit gerade von den Spänen zusammengehalten wird. Nach einer Standzeit von 24 Stunden in einer Atmosphäre von 70 % relativer Luftfeuchtigkeit werden die Späne von der Platte durch Kippen heruntergeschüttelt. Es hinterbleibt der deutlich sichtbare Umriß des angetrockneten wäßrigen Mediums. An den Kontaktstellen der Späne mit der Platte haben sich je nach Korrosivität der Flüssigkeit Rostmarken kleinerer oder größerer Ausdehnung ausgebildet, die auch zu einer geschlossenen Rostschicht zusammengewachsen sein können. Die Beurteilung kann durch visuelles Abschätzen in Flächenprozent Rostanteil geschehen.The solutions or emulsions to be tested for their corrosion behavior are applied to the piles of chips by means of a measuring pipette in such a quantity that the liquid reaching the cast steel plate comes straight from the Chips are held together. After standing for 24 hours in an atmosphere of 70% relative humidity, the chips are shaken off the plate by tilting. The clearly visible outline of the dried aqueous medium remains. Depending on the corrosiveness of the liquid, rust marks of smaller or larger dimensions have formed at the contact points of the chips, which can also have grown together to form a closed rust layer. The assessment can be made by visually estimating the percentage of rust in the area.
Eine weitere Korrosionsprüfung besteht in der Grauguß-Filterprobe. Verwendet wird eine Petrischale von ca. 10 cm Innendurchmesser mit passender Deckelschale. In die Petrischale legt man ein Schwarzband-Rundfilter. Auf das Filter werden mit einem passenden Löffel 5 bis 10 g grobe Grauguß GG-20-Späne so verteil, daß ein gleichmäßiger Haufen in der Mitte entsteht, der ringsum ca. 1,5 cm vom Rand Abstand hat. Die Späne haben ca. 5 bis 8 mm Länge und müssen aus sauberem Grauguß-GG-20-Material ohne Verwendung von Borhöl oder sonstigen Kühlschmiermitteln gewonnen sein. Alle feinen Bestandteile müssen abgesiebt werden.A further corrosion test consists in the gray cast iron filter sample. A petri dish with an inner diameter of approx. 10 cm is used with a suitable lid dish. A black band round filter is placed in the Petri dish. A suitable spoon is used to distribute 5 to 10 g of coarse gray cast iron GG-20 chips onto the filter in such a way that a uniform heap is formed in the middle, which is around 1.5 cm away from the edge. The chips have a length of approx. 5 to 8 mm and must be obtained from clean gray cast iron GG-20 material without the use of boron oil or other cooling lubricants. All fine components must be screened.
Von der auf Korrosivität zu prüfenden Lösung oder Emulsion werden jeweils 5 ml gleichmäßig mit einer Meßpipette auf die Späne gegeben. Der pH-Wert der Prüfflüssigkeit wird registriert, da er für die Beurteilung von wesentlicher Bedeutung ist. Er kann auf einen bestimmten Standardwert, z.B. 8,5, gestellt sein. Nach der Befeuchtung wird die Deckelschale aufgesetzt und 2 Stunden unter normalen Laborbedingungen bei 23 bis 25°C und ca. 70 % relativer Luftfeuchtigkeit stehen gelassen. Danach wird der Deckel abgenommen und das Filter kurz umgekehrt und auf die Oberfläche von Leitungswasser gelegt, wodurch es von den Spänen befreit wird. Gleich darauf wird das so befreite Filterpapier mit einer Indikatorlösung folgender Zusammensetzung besprüht und dadurch durchtränkt:
- 1 g Kaliumhexacyanoferat (III)
- 30 g Kochsalz
- 1 1 Wasser
- 1 g potassium hexacyanoferate (III)
- 30 g of table salt
- 1 1 water
Dann läßt man den Indikator 17 Sekunden lang an der Luft einwirken. Schließlich wird sorgfältig in fließendem Trinkwasser gespült und an mäßig warmem Ort an der Luft getrocknet. Auf dem Filterpapier ergeben sich nach dieser Prozedur, je nach Korrosivität des Mediums, braungelbe, gelbe und/oder blaugrüne Flecken verschiedener Intensität, wobei die braungelbe oder gelbe Farbe ungünstiger zu bewerten ist. Ein einwandfreies Verhalten zeigt sich durch Fehlen jeglicher Braun- oder Gelbfärbung und allenfalls spurenweisem Vorhandensein von blaugrünen,blassen Flecken an. Die Filter sind völlig farbstabil und können deshalb zur Dokumentation dienen. Eine Bewertungsskala kann folgendermaßen lauten:
- sehr schlecht: intensive große, überwiegend gelb-(--) braune Flecken;
- schlecht: intensive große Flecken mit etwa (-) gleichem gelbbraunen und blaugrünen Anteil;
- mittelmäßig: abgeblaßte mittelgroße Flecken mit (+-) etwa gleichem gelben und blaugrünen Anteil;
- gut: stark abgeblaßte, kleine (Stecknadel-(+) kopfgroße) Flecken mit überwiegendem Anteil an blaugrün;
- sehr gut: keinerlei Flecken oder höchstens sehr (++) wenige, sehr kleine blaßblaucrüne Flecken.
- very bad: intense large, mostly yellow - (-) brown spots;
- bad: intense large spots with about (-) the same yellow-brown and blue-green part;
- moderate: faded medium-sized spots with (+ -) approximately the same yellow and blue-green portion;
- good: heavily faded, small (pin - (+) head-sized) spots with a predominance of blue-green;
- very good: no stains or at most very (++) few, very small pale blue-crimson stains.
Es wurde in Anlehnung an die DIN 53 902 die Schlagmethode verwendet. Zur Prüfung genügte das einfach Prüfungsverfahren, bei dem der Stempel mit der Lochplatte per Hand 30 mal in 30 s gleichmäßig auf- und abgeführt und dann vorsichtig herausgezogen wird (IG-Schlagmethode). Das Schaumvolumen wird an dem graduierten Schaumzylinder nach 1, 5 und 10 min in ml abgelesen. Von Wichtigkeit sind daneben Angaben über Temperatur, Konzentration und Wasserhärte.
Claims (3)
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
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DE2758123 | 1977-12-24 | ||
DE19772758123 DE2758123A1 (en) | 1977-12-24 | 1977-12-24 | CORROSION PROTECTION AGENTS IN Aqueous SYSTEMS |
Publications (2)
Publication Number | Publication Date |
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EP0002780A1 true EP0002780A1 (en) | 1979-07-11 |
EP0002780B1 EP0002780B1 (en) | 1980-11-26 |
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ID=6027361
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Application Number | Title | Priority Date | Filing Date |
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EP78101757A Expired EP0002780B1 (en) | 1977-12-24 | 1978-12-19 | Use of corrosion inhibitors in aqueous systems |
Country Status (3)
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US (1) | US4207285A (en) |
EP (1) | EP0002780B1 (en) |
DE (2) | DE2758123A1 (en) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE2943963A1 (en) * | 1979-10-31 | 1981-05-14 | Basf Ag, 6700 Ludwigshafen | Iron corrosion inhibition - with aq. system contg. alkanolamine salt(s) of alkenyl succinic acid(s) |
EP0222311A2 (en) * | 1985-11-13 | 1987-05-20 | Henkel Kommanditgesellschaft auf Aktien | Use of alkoxy-hydroxy-substituted fatty acids as corrosion inhibitors in oils and emulsions containing oil |
Families Citing this family (13)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
IT1098305B (en) * | 1978-06-02 | 1985-09-07 | Snam Progetti | ANTI-RUST FOR AQUOUS SYSTEMS AND ANTI-RUST LUBRICANT COMPOSITION |
DE2908301A1 (en) * | 1979-03-03 | 1980-09-18 | Basf Ag | LOW-FOAM CORROSION INHIBITORS WITH ANTIMICROBIAL PROPERTIES THAT CONTAIN BORIC ACID-ALKANOLAMINE REPRODUCTION PRODUCTS AS AN EFFECTIVE PRINCIPLE |
DE2940258A1 (en) * | 1979-10-04 | 1981-04-16 | Hoechst Ag, 6000 Frankfurt | HARDWATER-STABLE CORROSION PROTECTIVE |
DE3032226A1 (en) * | 1980-08-27 | 1982-04-01 | Henkel KGaA, 4000 Düsseldorf | METHOD AND MEANS FOR PASSIVATING IRON AND STEEL SURFACES |
DE3047304A1 (en) * | 1980-12-16 | 1982-07-29 | Basf Ag, 6700 Ludwigshafen | USE OF POLYHYDROXY-POLYALKYLENE-POLYAMINE SALTS OF MALEINAMID ACIDS AS A CORROSION PROTECTANT IN WATER-IN-OIL EMULSIONS |
US4379063A (en) * | 1981-02-20 | 1983-04-05 | Cincinnati Milacron Inc. | Novel functional fluid |
DE3222996A1 (en) * | 1981-06-22 | 1983-03-03 | Basf Ag, 6700 Ludwigshafen | Alkanolamine salts of cyclic amido acids and their use as anticorrosion agents in aqueous systems |
US4473491A (en) * | 1981-06-22 | 1984-09-25 | Basf Aktiengesellschaft | Alkanolamine salts of cyclic amide acids and their use as metal corrosion inhibitors in aqueous systems |
DE3237109A1 (en) * | 1982-10-07 | 1984-04-12 | Basf Ag, 6700 Ludwigshafen | USE OF AMINE SALTS OF MALEINAMID ACIDS AS INHIBITORS AGAINST THE CORROSION OF CO (DOWN ARROW) 2 (DOWN ARROW) AND H (DOWN ARROW) 2 (DOWN ARROW) S IN WATER-IN-OIL EMULSIONS |
DE3341013A1 (en) * | 1983-11-12 | 1985-05-23 | Henkel KGaA, 4000 Düsseldorf | AMBER ACID MONO-DIALKYLAMIDES AS WATER-SOLUBLE CORROSION PROTECTORS |
DE3416120A1 (en) * | 1984-04-30 | 1985-10-31 | Henkel KGaA, 4000 Düsseldorf | BENZOYLALANINE AND THEIR USE AS CORROSION INHIBITORS FOR AQUEOUS SYSTEMS |
DE3521116A1 (en) * | 1985-06-13 | 1986-12-18 | Henkel KGaA, 4000 Düsseldorf | SPECIAL BENZOYLALANINE AND THEIR USE AS CORROSION INHIBITORS FOR AQUEOUS SYSTEMS |
DE3609401A1 (en) * | 1986-03-20 | 1987-09-24 | Henkel Kgaa | WATER-SOLUBLE MIXTURES OF FATTY ACID-AMMONIUM SALTS AND POLYOL FATTY ACIDS OR THEIR ALKALI OR AMMONIUM SALTS, METHOD FOR THE PRODUCTION THEREOF AND THEIR USE AS CORROSION INHIBITORS IN AQUEOUS SYSTEMS |
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- 1978-12-19 DE DE7878101757T patent/DE2860352D1/en not_active Expired
- 1978-12-19 EP EP78101757A patent/EP0002780B1/en not_active Expired
- 1978-12-20 US US05/971,234 patent/US4207285A/en not_active Expired - Lifetime
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US2699427A (en) * | 1952-10-02 | 1955-01-11 | Gulf Oil Corp | Mineral oil compositions containing amidic acids or salts thereof |
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DE2943963A1 (en) * | 1979-10-31 | 1981-05-14 | Basf Ag, 6700 Ludwigshafen | Iron corrosion inhibition - with aq. system contg. alkanolamine salt(s) of alkenyl succinic acid(s) |
EP0222311A2 (en) * | 1985-11-13 | 1987-05-20 | Henkel Kommanditgesellschaft auf Aktien | Use of alkoxy-hydroxy-substituted fatty acids as corrosion inhibitors in oils and emulsions containing oil |
EP0222311A3 (en) * | 1985-11-13 | 1989-05-03 | Henkel Kommanditgesellschaft Auf Aktien | Use of alkoxy-hydroxy-substituted fatty acids as corrosion inhibitors in oils and emulsions containing oil |
Also Published As
Publication number | Publication date |
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US4207285A (en) | 1980-06-10 |
EP0002780B1 (en) | 1980-11-26 |
DE2758123A1 (en) | 1979-07-05 |
DE2860352D1 (en) | 1981-02-12 |
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