EP0002530A1 - Use of acid esters of phosphoric acids and alkoxylated aliphatic polyols as corrosion inhibitors and lubricants - Google Patents

Use of acid esters of phosphoric acids and alkoxylated aliphatic polyols as corrosion inhibitors and lubricants Download PDF

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Publication number
EP0002530A1
EP0002530A1 EP78101697A EP78101697A EP0002530A1 EP 0002530 A1 EP0002530 A1 EP 0002530A1 EP 78101697 A EP78101697 A EP 78101697A EP 78101697 A EP78101697 A EP 78101697A EP 0002530 A1 EP0002530 A1 EP 0002530A1
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EP
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Prior art keywords
parts
phosphoric acid
acid esters
oxide
lubricants
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EP78101697A
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German (de)
French (fr)
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EP0002530B1 (en
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Karl-Heinz Dr. Beyer
Klaus Dr. Wulz
Elmar Getto
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BASF SE
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BASF SE
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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
    • C23F11/167—Phosphorus-containing compounds
    • C23F11/1673—Esters of phosphoric or thiophosphoric acids
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M137/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing phosphorus
    • C10M137/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing phosphorus having no phosphorus-to-carbon bond
    • C10M137/04—Phosphate esters
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2225/00—Organic macromolecular compounds containing phosphorus as ingredients in lubricant compositions
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2225/00—Organic macromolecular compounds containing phosphorus as ingredients in lubricant compositions
    • C10M2225/02—Macromolecular compounds from phosphorus-containg monomers, obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2010/00—Metal present as such or in compounds
    • C10N2010/02—Groups 1 or 11
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2010/00—Metal present as such or in compounds
    • C10N2010/04—Groups 2 or 12

Definitions

  • the invention relates to the use of acidic phosphoric acid esters as anticorrosive agents for metals, the alkonol component being curon-celinated alkoxylates of polyhydric alcohols.
  • a certain reduction in the tendency to corrosion is often achieved by setting a stronger alkaline pH value, by adding alkali hydroxides or alkaline salts such as soda, borax, alkali phosphates, etc., or also by organic bases (amines).
  • a noticeable reduction in the corrosiveness of the aqueous medium is only achieved in this way at pH values above 9.5 to 10. In these cases, the effect is by no means sufficient, especially if the metal surface has to be passivated for a longer period of time after the contact has ended must be achieved with the aqueous medium.
  • oxidizing inorganic salts such as sodium chromate or sodium nitrite, but also nitric acid itself, cause real passivation.
  • toxicity and wastewater laws today largely prohibit the use of these compounds.
  • the layer-forming passivation by means of suitable organic compounds, which in the neutral to more alkaline pH range of interest are mostly anicnic, but also nonicnic or at most weakly katicnic in character, is generally applicable.
  • the alkali or amine salts of straight-chain aliphatic, saturated and unsaturated carboxylic acids can be mentioned.
  • the salts of oleic acid have been particularly popular.
  • the salts of such aliphatic carboxylic acids containing carbonamide or sulfonamide groups, e.g. the salts of oleoyl sarcoside or alkanesulfonamidocarboxylic acids have long been known to be effective corrosion inhibitors for aqueous media against iron and steel.
  • the products with carbonamide groups are less hard, carbonamide groups are less hardy, but not low-foaming, which limits their usability.
  • alkyl and polyether chain length By changing the alkyl and polyether chain length, different oil and mass solubility can be set for the acidic products and the neutralized products.
  • These acidic phosphoric acid esters are neutralized with alkali hydroxides, alkaline earth hydroxides or organic bases such as amines (e.g. alkanolamines).
  • amines e.g. alkanolamines
  • solubility in oil or water can be changed.
  • Certain phosphate esters that have been developed in this direction can be regarded as high-pressure lubricants (EP additives).
  • EP additives high-pressure lubricants
  • the lubricating effect of the corresponding liquids must be brought up to the required level by adding special lubricating additives.
  • these lubricating additives promote corrosion, but at least they do not protect against corrosion. The combination of corrosion protection and lubrication is therefore an important and decisive advantage of phosphoric acid esters.
  • the aim of the invention now consists in phosphoric acid esters that combine corrosion inhibition, lubrication and low foaming as acids or salts. A targeted grading of these third properties should also be possible.
  • the preparation of the acidic esters is simple and is carried out by esterifying the alkoxylates - to be defined further below - with orthophosphoric acid (H 3 PO 4 ) phosphorus pentoxide or polyphosphoric acid in a manner known per se. It is preferred to use phcphpentoxide or polyphosphoric acid in order to avoid the time-consuming removal of the reactive water formed during the esterification.
  • the proportion of polyphosphoric acid or phosphorus pentoxide should be 10 to 15 mol% above the stoichiometric amount required.
  • the esterification is otherwise conveniently carried out in the equivalent ratio of alcohol component to phosphoric acid, such as 2: 1 to 1: 2. L
  • the acid content in the ester mixtures can be neutralized with bases.
  • All common inorganic bases such as NaOH, KOH, Ca (OH) 2 , Ba (OH) 2 , NH 3 or organic bases such as C 1 -C 4 -alkylamines, morpholine and preferably mono-, di- or tri are used for this -C 2 - to C 4 -alkanolamines such as triethanolamine or triisopropanolamine.
  • the amount of base can vary within certain limits.
  • An Mcl ratio of ester: base such as 1: 1 to 1: 4 is expediently chosen.
  • alxylene oxide content in the alkoxylation products formed has a total molecular weight of 200 to 8,000, preferably 1,000 to 4,000.
  • Propylene oxide, butylene oxide or in mixtures can be used as alkylene oxides.
  • Ethylene oxide can also be used, but only in a mixture with prepylene oxide and / or butylene oxide.
  • the alcohols are preferably reacted with propylene oxide alone, butylene oxide alone, with propylene oxide and ethylene oxide or with ethylene oxide, propylene oxide and butylene oxide.
  • alkylene oxides are used, the addition can take place in blocks, that is to say in succession, or by niche gassing, the individual alkylene residues being statistically distributed in the molecule in the latter case.
  • the proportions - if several alkylene oxides are used - are chosen so that the end products (esters) foam as little as possible.
  • the nol ratio of propylene oxide and ethylene oxide should be 5: 5 to 9: 1, preferably 7: 3 to 9: 1; in the case of the use of prepylene oxide, butylene oxide and ethylene oxide, ratios of 5: 4: 1 to 0: 1: 1 are expediently selected, i.e. At least 50 mol% of propylene oxide is present in the batch.
  • the alkoxylates can be obtained by known methods from the basic alkols by reacting them with the alkylene oxides at temperatures from 30 ° C. to 160 ° C. under the influence of alkaline catalysts. This operation is well known; it is part of the basic knowledge of the professional world.
  • the acidic esters obtained after the esterification of the alkoxylates with phosphoric acid can be used in numerous media as excellent low-foaming corrosion protection agents. They can be used in certain quantities, depending on the type of application. One uses, based on the corresponding liquid medium in question, 0.1-5.0 wt .-% or occasionally more, based on the medium, of phosphoric acid esters according to the invention or their salts.
  • Examples of applications are: lubricating oils, anti-corrosion oils, heat transfer, cold transfer and hydraulic fluids, mineral oil-free water-soluble cooling lubricants, metal processing emulsions, echo oils, grinding and polishing emulsions and dispersions, metal cleaners of various types, synthetic waxes, anti-corrosive agents and anti-corrosion agent, surface treatment agents, anti-corrosion agents, passivation agents the chemical industry and other branches of industry.
  • the prebondon according to the invention also have nourishing and solubilizing properties. They can therefore be used in all cases where these properties are used in conjunction with low foam, lubrication and / or corrosion protection.
  • a mixed alkoxylate composed of 10 parts of dipropylene glycol, 32.9 parts of ethylene oxide, 186.6 parts of propyleneoside and 0.5 part of KOH are mixed with 27.1 parts of polyphosphoric acid 84% at 40-50 ° C. and then for 8 hours stirred at 95-100 ° C. touched. 256 parts of a dark brown oil are obtained.
  • 211 parts of a mixed alkoxylate (statistical distribution) of 10.5 parts of trinethylolpropane, 150 parts of ethyl oxide, 50 parts of propylene oxide and 0.5 part of KOH are at 40-50 ° C with 23 parts of polyphosphoric acid
  • polyphosphoric acid 84 70 parts are added at 40-50 ° C to 765.5 parts of a block polymer composed of 6 parts of ethylenediamine, 136.5 parts of ethylene oxide (4-fold ethoxylated ethylenediamine as starting product), 622.5 parts of propylene oxide and 0.5 part of KOH % and then stir for 8 hours
  • Previously known types of phosphoric acid esters and products according to the invention according to the examples were tested for corrosion protection, low foaming and lubrication.
  • the corrosion protection effect was compared in the Herberts test and in the gray cast iron test.
  • the Herberts test is carried out based on DIN 51360, Part 1.
  • a pile of scarfs is placed on a freshly ground gray cast iron plate and wetted with the test liquid. After 24 hours, the rust on the gray cast iron plate is indicated in% of the total wetted area.
  • the gray cast iron test is carried out in accordance with DIN 51360, part 2.
  • Gray cast iron shavings are placed on a filter paper and wetted with the test liquid. After 2 hours the corrosion products are sampled on the filter paper. The result is on a scale from very good to very bad. The exact execution of the two tests can be seen from DT-OS 23 57 951.
  • the foam behavior is tested in accordance with DIN 53902.
  • the test liquid is poured into a glass tube and foam is beaten with a perforated punch under defined conditions.
  • the test result is given in ml foam after a certain time. More details can also be found in DT-OS 23 57 951.
  • the lubricating effect was checked on the friction wear machine according to Reichent. It is a test in which a cylinder and a ring rub against each other, WHERE an elliptical recess is ground out of the softer cylinder.
  • the ground surface is a measure of the lubricating effect (EP effect) of the product, in the solution of which the ring runs during the test. The larger the surface that is ground out, the worse the lubricating effect.
  • the mixing ratios required for the triethanolamine salt are listed in the table. These are weight ratios.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Lubricants (AREA)
  • Preventing Corrosion Or Incrustation Of Metals (AREA)

Abstract

1. The use of acidic esters of acids of phosphorus prepared from acids of phosphorus and aliphatic diols, triols or tetrols of 2 to 8 carbon atoms which have been alkoxylated with propylene oxide and/or butylene oxide, the proportions of alkylene oxide together having molecular weights of from 200 to 8,000, or salts thereof as low-foam anticorrosive agents and lubricants for metals.

Description

Die Erfindung betrifft die Verwendung saurer Phosphersäureester als Korrcsionsschutzmittel für Metalle, wobei die Alkonolkomponente curon celinierte Alkoxylate menrwertiger Alkohole dargestellt wird.The invention relates to the use of acidic phosphoric acid esters as anticorrosive agents for metals, the alkonol component being curon-celinated alkoxylates of polyhydric alcohols.

Die Gefahr der Korrosion besteht in vielen Fällen auf zahlreichen Anwendungsgebieten, bei denen Eisen, Stahl, andere eisenhaltige Netalle, aber auch Leichtmetalle, ie Aluminium, in Kontakt mit Wasser oder anorganisch-oder organisch-wäßrigen Lösungen stehen.In many cases there is a risk of corrosion in numerous fields of application in which iron, steel, other ferrous metals, but also light metals, ie aluminum, are in contact with water or inorganic or organic-aqueous solutions.

Die Korrosivität des betreffenden wäßrigen Mediums gegenüber Teilen aus Eisen, Eisenlegierungen, Stahl oder Aluminium, wie zum Beispiel Maschinen, Behälter, Rohre etc. muß vielfach durch korrosicnsschützende Zusätze vermindert oder ganz aufgehoben werden. Eine gewisse Verminderung der Korrosionsneigung erreicht man häufig schon durch Einstellung eines stärkeren alkalischen pH-Wertes, durch Zusatz von Alkalihydroxiden oder alkalisch reagierenden Salzen wie Soda, Borax, Alkaliphosphaten u.a. oder auch von organischen Basen (Aminen).The corrosiveness of the aqueous medium in question towards parts made of iron, iron alloys, steel or aluminum, such as machines, containers, pipes, etc., must often be reduced or completely eliminated by means of anti-corrosive additives. A certain reduction in the tendency to corrosion is often achieved by setting a stronger alkaline pH value, by adding alkali hydroxides or alkaline salts such as soda, borax, alkali phosphates, etc., or also by organic bases (amines).

Eine merkliche Verminderung der Korrosivität des wäßrigen\ Mediums erreicht man auf diese Weise jedoch erst bei pH-Werten oberhalb von 9,5 bis 10. In diesen Fällen ist der Effekt keineswegs ausreichend, insbesondere, wenn eine länger währende Passivierung der Metalloberfläche nach Beendigung des Kontakts mit dem wäßrigen Medium erreicht werden muß. Oxidierende anorganische Salze wie Natriumchromat oder Natriumnitrit, aber auch Salpetersäure selbst bewirken in geeigneten Fällen eine echte Pasivierung. Toxizität und Abwassergesetze verbieten heute jedoch weitgehend den Einsatz dieser Verbindungen. Die schichtbildende Passivierung mittels geeigneter organischer Verbindungen, die im interessierenden neutralen bis stärker alkalischen pH-Bereich meistens anicnischen, aber auch nichticnischen oder höchstens schwach katicnischen Charakter haben, ist dagegen aligemein anwendbar.A noticeable reduction in the corrosiveness of the aqueous medium is only achieved in this way at pH values above 9.5 to 10. In these cases, the effect is by no means sufficient, especially if the metal surface has to be passivated for a longer period of time after the contact has ended must be achieved with the aqueous medium. In suitable cases, oxidizing inorganic salts such as sodium chromate or sodium nitrite, but also nitric acid itself, cause real passivation. However, toxicity and wastewater laws today largely prohibit the use of these compounds. The layer-forming passivation by means of suitable organic compounds, which in the neutral to more alkaline pH range of interest are mostly anicnic, but also nonicnic or at most weakly katicnic in character, is generally applicable.

Vom anionischen Typ sind die Alkali- oder Aminsalze geradkettiger aliphatischer, gesättigter und ungesättigter Carbonsäuren zu nennen. Die Salze der Ölsäure haben sich besonders eingeführt. Auch die Salze von solchen aliphatischen Carbonsäuren, die Carbonamid- oder Sulfonamidgruppen enthalten, z.B. die Salze des Oleoylsarkosids cder Alkansulfonamidocarbonsäuren, sind seit längerer Zeit als wirksame Kcrrcsionsinhibitoren für wäßrige Medien gegenüber Eisen und Stahl bekannt.From the anionic type, the alkali or amine salts of straight-chain aliphatic, saturated and unsaturated carboxylic acids can be mentioned. The salts of oleic acid have been particularly popular. The salts of such aliphatic carboxylic acids containing carbonamide or sulfonamide groups, e.g. the salts of oleoyl sarcoside or alkanesulfonamidocarboxylic acids have long been known to be effective corrosion inhibitors for aqueous media against iron and steel.

Wie aus der DAS 1 298 672 bekannt ist, werden neuerdings auch am Kern substituierte Arylsulfonamidocarbonsäuren bzw. deren Salze eungesetzt.As is known from DAS 1 298 672, arylsulfonamidocarboxylic acids or their salts substituted on the nucleus have recently also been used.

Alle diese Verbindungen haben aber auch beträchliche Nachteile. Fettsäuresalze, besonders die Salze der Ölsäure, besitzen eine gewisse Empfindlichkeit gegenüber r Wasserhärte, was die ohnehin nicht so günstige Kor- rosionsschutzwirkung noch herabmindert.However, all of these connections also have considerable disadvantages. Fatty acid salts, especially the salts of oleic acid, have a certain sensitivity to water hardness, which is not so cheap. corrosion protection still reduced.

Die Produkte mit Carbonamidgruppen sind weniger härteemp-Carbonamidgruppen sindweniger härt findlich, dafür aber nicht schaumarm, was ihre Einsetzbarkeit begrenzt.The products with carbonamide groups are less hard, carbonamide groups are less hardy, but not low-foaming, which limits their usability.

Die am Kern substituierten Arylsuifonamidcarbonsäuren bzw. deren Salze sind nur dann gleichseitig korrosionsschützend und genügend schaumarm, wenn sie am Amidstickstcff alkyliert sind. Dieses führt jedoch zu seinem zusatzlichen fabrikaterischen Aufwand.

Figure imgb0001
ponente and Neutralisationsmittel können die verschiedensten Effekte eingestellt werden. Mach den Stand der Technik allgemein bekannt sind folgende Typen:

  • - Phosphorsäureester mit kurzzeitigen Alkyl-Rest (z.E. Isobutyl-)
  • Phosphorsäureester mit längerkettigen Alkyl-Rest (Ester der Phosphcrsäure mit Fettalkcholen)
  • Phosphorsäureester mit Alkylphenol-Rest (z.B. Nonylpnenol-)
  • - Phosphorsäureester von äthcxylierten Alkoholen (z.B. Fettalkoholäthoxylat-)
  • - Phosphorsäureester von äthoxylierten Alkylphenolen (z.B. Nonylphenoläthoxylat-)
  • - Phosphorsäureester von äthoxylierten und propoxylierten Pettalkoholen oder Alkylphenolen, wobei die Alkylencxide in statistischer Verteilung oder als Blockcopolymerisate angelagert sein können.
  • Phosphorsäureester von alkoxylierten einwertigen Alkoholen, bei denen auch Butylenoxid in die Polyätherkette eingebaut wurde.
The arylsulfonamide carboxylic acids or their salts substituted on the core are only corrosion-protecting on the same side and are sufficiently low-foaming if they are alkylated on the amide nitrogen. However, this leads to additional manufacturing costs.
Figure imgb0001
Component and neutralizing agent can be set to a wide variety of effects. The following types are generally known in the art:
  • - Phosphoric acid esters with a short-term alkyl residue (eg isobutyl)
  • Phosphoric acid esters with a long-chain alkyl residue (esters of phosphoric acid with fatty alcohols)
  • Phosphoric acid ester with alkylphenol residue (e.g. nonylpnenol)
  • - Phosphoric acid esters of ethoxylated alcohols (e.g. fatty alcohol ethoxylate)
  • - phosphoric acid esters of ethoxylated alkylphenols (e.g. nonylphenol ethoxylate)
  • - Phosphoric acid esters of ethoxylated and propoxylated pett alcohols or alkyl phenols, it being possible for the alkylene oxides to be present in statistical distribution or as block copolymers.
  • Phosphoric acid esters of alkoxylated monohydric alcohols, in which butylene oxide has also been incorporated into the polyether chain.

Durch Veränderung der Alkyl- und Polyäther-Kettenlänge können unterschiedliche öl- und Masserlösliehkeiten der sauren Produkte und der neutralisierten Produkte eingestellt werden. Diese sauren Phosphorsäureester werden mit Alkalihydroxiden, Erdalkalihydroxiden oder organischen Basen wie Aminen (z.B. Alkanolaminen) neutralisiert. Je nach Anforderung läßt sich dadurch die Löslichkeit in öl oder Wasser verändern.By changing the alkyl and polyether chain length, different oil and mass solubility can be set for the acidic products and the neutralized products. These acidic phosphoric acid esters are neutralized with alkali hydroxides, alkaline earth hydroxides or organic bases such as amines (e.g. alkanolamines). Depending on the requirements, the solubility in oil or water can be changed.

Der Vorteil der Phosphorsäu7reester resenüoer deren Korrcsionsinhibivoren besteht darin, daß außer ihrer in wäßrigen und nichtwäßrigen Systemen gleichermaßen auftretenden Kcrrcsicnsschutzwirkung auch eine gute Schmierwirkung eintritt, die ebenfalls in wäßrigen und nichtwäßrigen Systemen zur Geltung kommtThe advantage of phosphoric acid esters, as well as their corrosion inhibitors, is that, in addition to their corrosion protection effect, which occurs equally in aqueous and non-aqueous systems, there is also a good lubricating effect, which is also effective in aqueous and non-aqueous systems

Bestimmte Phcsphcrsäureester, die in dieser Richtung entwickelt wurden, können als ausgesprochene Hcchdruckschmiermittel (EP-Additive) gelten. Bei anderen Korrosionsinhibitoren muß die Schmierwirkung der entsprechenden Flüssigkeiten durch Zusätze von speziellen Schmieradditiven auf den geforderten Stand gebracht werden. Diese Schmieradditive sind in den meisten Fällen korrcsicnsfördernd, zumindest aber nicht korrcsionsschützend. Die Verbindung von Korrosionsschutz und Schmierwirkung ist darum ein wichtiger und entscheidender Vorteil der Phosphorsäureester.Certain phosphate esters that have been developed in this direction can be regarded as high-pressure lubricants (EP additives). In the case of other corrosion inhibitors, the lubricating effect of the corresponding liquids must be brought up to the required level by adding special lubricating additives. In most cases, these lubricating additives promote corrosion, but at least they do not protect against corrosion. The combination of corrosion protection and lubrication is therefore an important and decisive advantage of phosphoric acid esters.

Das Hauptproblem, das bisher bei solchen Phosphorsäureestern bestand, ist ihre starke Schaumneigung. Gerade in wäßrigen Formulierungen und in Emulsionen konnten sie daher bisher nicht in großem Ausmaß eingesetzt werden. Zwar kann der entstehende Schaum durch entsprechende Mengen Schaumverhüter unterdrückt werden; diese Lösung ist aber nur in wenigen Fällen anwendbar. Entweder wird dadurch die Wirtschaftlichkeit einer Rezeptur beeinträchtigt oder der Schaumverhüter hat Nebenwirkungen, die eine Anwendung ausschließen (z.B. Silikonentschäuner). Nun ist es zwar auch schon gelungen, Fhosphorsäureester herzustellen, deren Salze in wäßrigen Lösungen nur schwach schäumen, gleichzeitig verschlechtern sich aber, wie wir festgestellt haben, die Korrosionsschutz- und Schmiereigenschaften.The main problem that has previously existed with such phosphoric acid esters is their strong tendency to foam. So far it has not been possible to use them to a large extent, especially in aqueous formulations and in emulsions. The resulting foam can be suppressed by appropriate amounts of foam inhibitor; this solution is only applicable in a few cases. Either this affects the economy of a formulation or the foam inhibitor has side effects that preclude its use (e.g. silicone defoamers). Now it has already been possible to produce phosphoric acid esters, the salts of which foam only weakly in aqueous solutions, but at the same time, as we have found, the corrosion protection and lubrication properties deteriorate.

Das Ziel der Erfindung besteht nunmehr in Phosphorsäureestern, die als Säuren oder als Salse Korrosionsinhibierung, Schmierwirkung und Schaumarmut miteinander vereinden. Dabei soll außerdem eine gezielte Ab stufung dieser drel Eigenschaften möglich sein.The aim of the invention now consists in phosphoric acid esters that combine corrosion inhibition, lubrication and low foaming as acids or salts. A targeted grading of these third properties should also be possible.

Es wurde nun gefunden, daß mit sauren Phosphorsäureestern oder deren Salzen, deren Alkoholkomponente aus Alkcxylaten mehrwertiger Alkohole besteht, und die gemäß den Patentansprüchen definiert sind, dieses Ziel in optimaler Weise erreicht werden kann.It has now been found that acidic phosphoric acid esters or their salts, the alcohol component of which consists of alkoxylates of polyhydric alcohols, and which are defined in accordance with the patent claims, can achieve this goal in an optimal manner.

Die Herstellung der sauren Ester ist einfach und geschieht in der Weise, daß man die - weiter unten noch näher zu definierenden - Alkoxylate mit Orthophosphorsäure (H3PO4) Phosphorpentoxid oder Polyphosphorsäure in an sich bekannter Weise verestert. Man verwendet dabei vorzugsweise Phcsphcrpentoxid oder Polyphosphorsäure, un die zeitraubende Entfernung des bei der Veresterung entstehenden Reakticnswassers zu vermeiden. Hierbei sollte der Anteil an Polyphosphorsäure oder Phosphorpentoxid um 10 bis 15 Mol-% über der erforderlichen stöchiometrischen Menge liegen. Die Veresterung erfolgt sonst zweckmäßigerweise im Aquivalentverhältnis Alkoholkompcnente zu Phosphorsäure wie 2:1 bis 1:2. L The preparation of the acidic esters is simple and is carried out by esterifying the alkoxylates - to be defined further below - with orthophosphoric acid (H 3 PO 4 ) phosphorus pentoxide or polyphosphoric acid in a manner known per se. It is preferred to use phcphpentoxide or polyphosphoric acid in order to avoid the time-consuming removal of the reactive water formed during the esterification. The proportion of polyphosphoric acid or phosphorus pentoxide should be 10 to 15 mol% above the stoichiometric amount required. The esterification is otherwise conveniently carried out in the equivalent ratio of alcohol component to phosphoric acid, such as 2: 1 to 1: 2. L

Bei der Veresterung entstehen Mono- und Drestergemische, wohingegen die Triester praktisch nicht gebildet werden. Die Gemische werden deshalb auch als "saure Ester" bezeichnet. Der Säureanteil in den Estergemischen kann mit Basen neutralisiert werden. Hierfür kommen alle gängigen anorganischen Basen wie NaOH, KOH, Ca(OH)2, Ba(OH)2, NH3 oder organische Basen wie C1- bis C4-Alkylamine, Morpho- lin und bevorzugt Mono-, Di- oder Tri-C2- bis C4-alkanolamine wie Triäthanolamin oder Triisopropanolamin in Betracht. Die Menge an Base kann in gewissen Grenzen schwankeng zweckmäßigerweise wähls man ein Mclverhältnis Ester: Base wie 1:1 bis 1:4.

Figure imgb0002
During the esterification, mono- and drester mixtures are formed, whereas the triesters are practically not formed. The mixtures are therefore also referred to as "acidic esters". The acid content in the ester mixtures can be neutralized with bases. All common inorganic bases such as NaOH, KOH, Ca (OH) 2 , Ba (OH) 2 , NH 3 or organic bases such as C 1 -C 4 -alkylamines, morpholine and preferably mono-, di- or tri are used for this -C 2 - to C 4 -alkanolamines such as triethanolamine or triisopropanolamine. The amount of base can vary within certain limits. An Mcl ratio of ester: base such as 1: 1 to 1: 4 is expediently chosen.
Figure imgb0002

Diese Basisalkohole werden dann mit den definitionsge- mäßen Alkylenoxiden mit der Maßgabe alkoxyliert, daß der Alxylenoxid-Anteil in den entstandenen Alkoxylierungsprodukten ein Gesamtmolekulargewicht von 200 bis 8.000, vorzugsweise von 1.000 bis 4.000 aufweist. Als Alkylenoxide können Propylenoxid, Butylenoxid oder in Gemische eingesetzt werden.These basic alcohols are then alkoxylated with the alkylene oxides according to the definition, with the proviso that the alxylene oxide content in the alkoxylation products formed has a total molecular weight of 200 to 8,000, preferably 1,000 to 4,000. Propylene oxide, butylene oxide or in mixtures can be used as alkylene oxides.

Des weiteren kann auch Äthylenoxid, jedoch nur im Gemisch mit Prcpylenoxid und/oder Butylenoxid eingesetzt werden.Ethylene oxide can also be used, but only in a mixture with prepylene oxide and / or butylene oxide.

Vorzugsweise setzt man die Alkohole um mit Propylenoxid allein, Butylenoxid allein, mit Propylenoxid und Athylenoxid oder mit Athylenoxid, Propylenoxid und Butylenoxid.The alcohols are preferably reacted with propylene oxide alone, butylene oxide alone, with propylene oxide and ethylene oxide or with ethylene oxide, propylene oxide and butylene oxide.

Werden mehrere Alkylenoxide eingesetzt, dann kann die Anlagerung blockweise, also nacheinander, oder durch Nisch- begasung erfolgen, wobei im letzteren Fall die einzelnen Alkylenoreste statistisch im Molekül verteilt sind.If several alkylene oxides are used, the addition can take place in blocks, that is to say in succession, or by niche gassing, the individual alkylene residues being statistically distributed in the molecule in the latter case.

Die Mengenverhältnisse- falls mehrere Alkylenoxide eingesetst werden - werden so gewählt, daß die Endprodukte (Ester) möglichst wenig sahäumen. In Falle den Venwendung von Prcpylenoxid und Äthylenoxid sollte das Nolverhältnis von Propylenoxid und Äthylenoxid sollte das Nolverhältnis 5:5 bis 9:1, vorzugsweise 7:3 bis 9:1 betragen; im Falle der Verwendung von Prcpylenoxid, Butylenoxid und Athylenoxid wählt man zweckmäßigerweise Verhältnisse von 5:4:1 bis 0:1:1, d.h. Propylenoxid ist mindestens zu 50 Mol-% im Ansatz anwesend.The proportions - if several alkylene oxides are used - are chosen so that the end products (esters) foam as little as possible. In the case of the use of propylene oxide and ethylene oxide, the nol ratio of propylene oxide and ethylene oxide should be 5: 5 to 9: 1, preferably 7: 3 to 9: 1; in the case of the use of prepylene oxide, butylene oxide and ethylene oxide, ratios of 5: 4: 1 to 0: 1: 1 are expediently selected, i.e. At least 50 mol% of propylene oxide is present in the batch.

Die Alkcxylate können nach an sich bekannten Methoden aus den Basisalkcholen durch deren Umstzung mit den Alkylenoxiden bei Temperaturen von 30 °C bis 160 °C unter dem Einfluß alkalischer Katalysatoren erhalten werden. Diese Operation ist bekannt; sie gehört zum Grundwissen der Fachwelt.The alkoxylates can be obtained by known methods from the basic alkols by reacting them with the alkylene oxides at temperatures from 30 ° C. to 160 ° C. under the influence of alkaline catalysts. This operation is well known; it is part of the basic knowledge of the professional world.

Die nach der Veresterung der Alkoxylate mit Phosphorsäure erhaltenen sauren Ester sind in zahlreichen Medien als ausgezeicnnete schaumarme Korrosionsschutzmittel einsetzbar. Sie können in bestimmten Quantitäten eingesetzt werden, die sich nach der Art des Einsatzzweckes richten. Man verwendet, bezogen auf das entsprechende in Frage stehende flüssige Medium, 0,1-5,0 Gew.-% oder gelegentlich mehr, bezogen auf das Medium, an erfindungsgemäßen Phosphorsäureestern bzw. ihren Salzen.The acidic esters obtained after the esterification of the alkoxylates with phosphoric acid can be used in numerous media as excellent low-foaming corrosion protection agents. They can be used in certain quantities, depending on the type of application. One uses, based on the corresponding liquid medium in question, 0.1-5.0 wt .-% or occasionally more, based on the medium, of phosphoric acid esters according to the invention or their salts.

Anwendungsbeispiele sind: Schmieröle, Korrosionsschutzöle, Wärmeübertragungs-, Kälteübertragungs- und Hydraulikflüs- sigkeiten, mineralölfrcie wasserlösliche Kühlschmierstoffe, Metallbearbeitungsemulsicnen, Echröle, Schleif- und Polieremulsicnen bzw. -dispersicnen, Metallreiniger der verschiedensten Art, synthetische Walrmittel, korrosicnsschützende Oberflächenbehandlungsmittel, Kcrrcsicnsschutzemulsionen, Passivierungslösungen und Proxeßwässer der chemischer Industrie und anderer Industriezweige. Wie auch die bisher schon bekannten Fhcsphcrsäureester haben die erfindungogemäßen Vorbindungon auch

Figure imgb0003
scnaften und solubilisierende Eigenschaften. Sie können daher in allen Fällen eingesetzt werden, wo diese Eigenschaften in Verbindung mit der Schaumarmut, der Schmierwirkung und/oder dem Korrosionsschutz gebraucht werden.Examples of applications are: lubricating oils, anti-corrosion oils, heat transfer, cold transfer and hydraulic fluids, mineral oil-free water-soluble cooling lubricants, metal processing emulsions, echo oils, grinding and polishing emulsions and dispersions, metal cleaners of various types, synthetic waxes, anti-corrosive agents and anti-corrosion agent, surface treatment agents, anti-corrosion agents, passivation agents the chemical industry and other branches of industry. Like the previously known hydrofluoric acid esters, the prebondon according to the invention also have
Figure imgb0003
nourishing and solubilizing properties. They can therefore be used in all cases where these properties are used in conjunction with low foam, lubrication and / or corrosion protection.

Die in den nachfolgenden Beispielen angegebenen Teile sind Gewichtsteile:The parts given in the following examples are parts by weight:

Beispiel 1example 1

Zu 292,5 Teilen eines Propoxylates aus 10 Teilen Dipropylenglykol, 282 Teilen Propylenoxid und 0,5 Teilen KOH gibt man bei 40-50 °C 30,5 Teile Polyphosphorsäure 84 % und rührt anschließend 8 Stunden bei 95-100 °C. Man erhält 322 Teile eines dunkelbraunen Öls.To 292.5 parts of a propoxylate of 10 parts of dipropylene glycol, 282 parts of propylene oxide and 0.5 part of KOH, 30.5 parts of polyphosphoric acid 84% are added at 40-50 ° C. and the mixture is then stirred at 95-100 ° C. for 8 hours. 322 parts of a dark brown oil are obtained.

Beispiel 2Example 2

Zu 200,5 Teilen eines Propoxylates aus 13,4 Teilen Dipropylenglykol, 186,6 Teilen Propylenoxid und 0,5 Teilen KOH gibt man bei 40-50 °C 24,9 Teile Polyphosphorsäure 84 % und rührt anschließend 8 Stunden bei 95-100 °C nach. Man erhält 225 Teile eines rotbraunen Öls.To 200.5 parts of a propoxylate from 13.4 parts of dipropylene glycol, 186.6 parts of propylene oxide and 0.5 parts of KOH are added at 40-50 ° C 24.9 parts of polyphosphoric acid 84% and then stirred at 95-100 ° C for 8 hours. 225 parts of a red-brown oil are obtained.

Beispiel 3Example 3

1705 Teile eines Propoxylates aus 134 Teilen Dipropylenglykol, 1566 Teilen Propylenoxid und 1,5 Teilen KOH gibt man bei 40-50 °C 24,9 Teil Polyphosphorsäure 84 % versetzt und anschließend 8 Stunden bei 95-100 °C gerührt Man erhält 1948 Teile eines rotbraunen Öls.1705 parts of a propoxylate composed of 134 parts of dipropylene glycol, 1566 parts of propylene oxide and 1.5 parts of KOH are added at 40-50 ° C. 24.9 parts of polyphosphoric acid 84% and then stirred for 8 hours at 95-100 ° C. 1948 parts of one are obtained red-brown oil.

Beispiel 4Example 4

524 Teile eines Putoxylates aus 90 Teilen 1.4-Butandiol. 2 Teilen KOH und 432 Teilen 1,2-Butylenoxid werden bei 40-50 °C mit 73 Teilen Polyphcsphorsäure 84 % versetzt und 6 Studen bei 100 °C unter Vakuun (10-15 mm) gerührt. Man erhält 595 Teile eines dunkelbraunen Öls.524 parts of a putoxylate from 90 parts of 1,4-butanediol. 2 parts of KOH and 432 parts of 1,2-butylene oxide are mixed with 73 parts of polyphosphoric acid at 40-50 ° C with 84% and stirred for 6 hours at 100 ° C under vacuum (10-15 mm). 595 parts of a dark brown oil are obtained.

Beispiel 5Example 5

230 Teile eines Mischalkoxylates (statistische Verteilung) aus 10 Teiler Dipropylenglykol, 32,9 Teilen Äthylenoxid, 186,6 Teilen Propylenosid und 0,5 Teilen KOH werden bei 40-50 °C mit 27,1 Teilen Polyphosphorsäure 84 % versetzt and anschließend 8 Stunden bei 95-100 °C gerührt. gerührt. Man erhält 256 Teile eines dunkelbraunen Öls.230 parts of a mixed alkoxylate (statistical distribution) composed of 10 parts of dipropylene glycol, 32.9 parts of ethylene oxide, 186.6 parts of propyleneoside and 0.5 part of KOH are mixed with 27.1 parts of polyphosphoric acid 84% at 40-50 ° C. and then for 8 hours stirred at 95-100 ° C. touched. 256 parts of a dark brown oil are obtained.

Beisipel 6Example 6

Zu 200,4 Teilen eines Mischalkoxylates aus 10 Teilen Dipropylenglykol, 25 Teilen Äthylenoxid, 165 Teilen Propylenoxid und 0,4 Teilen KOH gibt man bei 40-50 °C 25 Teile Polyphosphorsäure 84 % und rührt anschließend 8 Stunden bei 95-100 °C. Man erhält 225 Teile eines dunkelbraunen öls.To 200.4 parts of a mixed alkoxylate composed of 10 parts of dipropylene glycol, 25 parts of ethylene oxide, 165 parts of propylene oxide and 0.4 part of KOH, 25 parts of 84% polyphosphoric acid are added at 40-50 ° C. and the mixture is then stirred 8 Hours at 95-100 ° C. 225 parts of a dark brown oil are obtained.

Beispiel 7Example 7

2000 Teile eines Blockalkoxylates aus 134 Teilen Dipropylenglykol, 1624 Teilen Propylenoxid, 237 Teilen Ätrylenoxid und 5 Teilen KOH werden bei 40-50 °C mit 197 Teilen Polyphosphcrsäure 84 % versetzt und anschließend 8 Stunden bei 95-100 °C gerührt.2000 parts of a block alkoxylate of 134 parts of dipropylene glycol, 1624 parts of propylene oxide, 237 parts of ethylene oxide and 5 parts of KOH are mixed with 197 parts of 84% polyphosphoric acid at 40-50 ° C. and then stirred at 95-100 ° C. for 8 hours.

Man erhält 2195 Teile eines rotbraunen Öls.2195 parts of a red-brown oil are obtained.

Beispiel 5Example 5

226,2 Teile eines Mischalkoxylaues (statistische Verteilung) aus 10,6 Teilen Diäthylenglykol, 64,5 Teilen Äthylenoxid, 107,5 Teilen Propylenoxid, 43 Teilen 1,2-Butylenoxid und 0,6 Teilen KOH werden bei 40-50 °C mit 26,9 Teilen Polyphcsphorsäure 84 % versetzt und anschließend226.2 parts of a mixed alkoxy liquor (statistical distribution) composed of 10.6 parts of diethylene glycol, 64.5 parts of ethylene oxide, 107.5 parts of propylene oxide, 43 parts of 1,2-butylene oxide and 0.6 part of KOH are mixed at 40-50 ° C 26.9 parts of polyphosphoric acid added 84% and then

8 Stunden bei 95-10C °C gerührt.Stirred at 95-10C ° C for 8 hours.

Man erhält 253 Teile eines rotbraunen Öls.253 parts of a red-brown oil are obtained.

Beispiel 9 Example 9

211 Teile eines Mischalkoxylates (statistische Verteilung) aus 10,5 Teilen Trinethylolpropan, 150 Teilen Äthyleoxid, 50 Teilen Propylenoxid und 0,5 Teilen KOH werden bei 40-50 °C mit 23 Teilen Polyphosphorsäure211 parts of a mixed alkoxylate (statistical distribution) of 10.5 parts of trinethylolpropane, 150 parts of ethyl oxide, 50 parts of propylene oxide and 0.5 part of KOH are at 40-50 ° C with 23 parts of polyphosphoric acid

84 % versetzt und anschließend 8 Stunden bei 95-100 °C gerührt.84% added and then stirred at 95-100 ° C for 8 hours.

Man erhält 233 Teile eines dunkelbraunen Öls.233 parts of a dark brown oil are obtained.

Beispiel 10Example 10

Zu 765,5 Teilen eines Blockpolymerisates aus 6 Teilen Äthylendiamin, 136,5 Teilen Äthylenoxid (4-fach äthoxyliertes Äthylendiamin als Ausgangsprodukt), 622,5 Teilen Propylenoxid und 0,5 Teilen KOH gibt man bei 40-50 °C 70 Teile Polyphosphorsäure 84 % und rührt anschließend 8 Stunden70 parts of polyphosphoric acid 84 are added at 40-50 ° C to 765.5 parts of a block polymer composed of 6 parts of ethylenediamine, 136.5 parts of ethylene oxide (4-fold ethoxylated ethylenediamine as starting product), 622.5 parts of propylene oxide and 0.5 part of KOH % and then stir for 8 hours

bei 95-100 °C nach.at 95-100 ° C after.

Man erhält 835 Teile eines dunkelbraunen Öls.835 parts of a dark brown oil are obtained.

Beispiel 11Example 11

1748 Teile eines Butoxylates aus 90 Teilen 1,4-Butandiol, 2 Teilen KOH und 1656 Teilen 1,2-Butylenoxid werden bei 40-50 °C mit 145 Teilen Polyphosphorsäure 84 % versetst und 6 Stunden bei 100 °C unter Vakuum (10-15 mm) gerührt. Man erhält 1890 Teile eines dunkelbraunen Öls.1748 parts of a butoxylate consisting of 90 parts of 1,4-butanediol, 2 parts of KOH and 1656 parts of 1,2-butylene oxide are mixed with 145 parts of polyphosphoric acid 84% at 40-50 ° C and 6 hours at 100 ° C under vacuum (10- 15 mm) stirred. 1890 parts of a dark brown oil are obtained.

Anwendungstechnische Prüfung der erfindungsgemäßen ProdukteApplication testing of the products according to the invention

Bisher bekannte Typen von Phosphorsäureestern und erfindungsgemäße Produkte entsprechend den Beispielen, wurden auf Korrosionsschutzwirkung, Schaumarmut und Schmierwirkung geprüft. Die Korrosionsschutzwirkung wurde im Herberts-Test und im Grauguß-Test verglichen. Der Herberts-Test wird in Anlehnung an DIN 51360, Teil 1, durchgeführt. Dabei wird ein Häufchen Schalspähne auf eine frisch geschliffene Graugußplatte gelegt und mit der Testflüssigkeit benetzt. Nach 24 Stunden wird der Rost auf der Graugußplatte in % der gesamten benetzten Fläche angegeben. Der Grauguß-Test wird in Anlehnung an DIN 51360, Teil 2, durchgeführt. Dabei werden Graugußspähne auf ein Filterpapier gelegt und mit der Testflüssigkeit benetzt. Nach 2 Stunden werden die Korrosionsprodukte auf dem Filterpapier abgemustert. Das Ergebnis wird in einer Skala von sehr gut bis sehr schlecht angegeben. Die genaue Durchführung der beiden Tests ist aus der DT-OS 23 57 951 ersichtlich.Previously known types of phosphoric acid esters and products according to the invention according to the examples were tested for corrosion protection, low foaming and lubrication. The corrosion protection effect was compared in the Herberts test and in the gray cast iron test. The Herberts test is carried out based on DIN 51360, Part 1. A pile of scarfs is placed on a freshly ground gray cast iron plate and wetted with the test liquid. After 24 hours, the rust on the gray cast iron plate is indicated in% of the total wetted area. The gray cast iron test is carried out in accordance with DIN 51360, part 2. Gray cast iron shavings are placed on a filter paper and wetted with the test liquid. After 2 hours the corrosion products are sampled on the filter paper. The result is on a scale from very good to very bad. The exact execution of the two tests can be seen from DT-OS 23 57 951.

Das Schaumverhalten wird in Anlehnung an DIN 53902 geprüft. Dabei wird die Prüfflüssigkeit in ein Glasrohr gefüllt und mit einen durchlöcherten Stempel unter definierten Bedingungen Schaum geschlagen. Angegeben wird das Prüfergebnis in ml Schaum nach einer bestimmten Zeit, Genaueres geht ebenfalls aus der DT-OS 23 57 951 hervor.The foam behavior is tested in accordance with DIN 53902. The test liquid is poured into a glass tube and foam is beaten with a perforated punch under defined conditions. The test result is given in ml foam after a certain time. More details can also be found in DT-OS 23 57 951.

Die Schmierwirkung wurde geprüft auf der Reibverschleiß-maschine nach Reichent, Es handelt sich um einen Test bei dem ein Zylinder und ein Ring aufeinander reiben, WObei aus dem weicheren Zylinder eine elipsenförmige Vertiefung herausgeschliffen wird. Die herausgeschliffene Flächde ist ein Maß für die Schmierwirkung (EP-Wirkung) des Produktes, in dessen Lösung der Ring beim Test läuft. Je größer die herausgeschliffene Fläche wird, desto schlechter ist die Shmierwirkung.The lubricating effect was checked on the friction wear machine according to Reichent. It is a test in which a cylinder and a ring rub against each other, WHERE an elliptical recess is ground out of the softer cylinder. The ground surface is a measure of the lubricating effect (EP effect) of the product, in the solution of which the ring runs during the test. The larger the surface that is ground out, the worse the lubricating effect.

In der beiliegenden Tabelle sind die Prüfergecnisse verzeichnet. Es wurden jeweils die Triäthanolamin-Salze der untersuchten Phosphorsäureester verglichen. Dabei wurde das Verhältnis Ester:Triäthanolamin so eingestellt, daß sich in den verdünnten wäßrigen Lösungen ein pH-Wert im Bereich von 8,3 bis 8, 8 ergibt. Die angegebenen Konzentrationen beziehen sich beim Herberts-Test und beim Grauguß-Test auf das Salz. Beim Schaumtest wurden 2 g/l eingesetzt, wobei jeweils auf enthaltenen Phosphorsäureester berechnet wurde. Die Abriebfläche in mm2 auf der Reichert-Reibverschleiß-Maschine wurde in 1 siger Lösung in Wasser von 10°d Härte gemessen, wobei sich die Konzentration auf enthaltenen Phosphorsäureester bezieht. Folgende Phosphorsäureester wurden miteinander verglichen:

  • Vergleich I Handelsprodukt (Phosphorsäureester eines Äthoxylierten, substituierten Aromaten).
  • Vergleich II Handelsprodukt (Phosphorsäureester eines substituierten Aromaten, der mit verschiedenen Alkylenoxiden umgesetzt ist).
  • Vergleich III Handelsproduzt (Phosphorsäureester eines kurzkettigen Fettalkohols mit überwiegendem Moncesteranteil).
  • Vergleich IV Handelsprodukt (Phosphorsäureester eines äthoxylierten und propoxylierten Fettalkohols).
  • Beispiel 1 Phosphorsäureeseter eines Polypropylenglykols mit dem Molekulargewich ca. 2230.
  • Beispiel 2 Phosphorsäureester von Polypropylenglykol mit dem Molekulargewicht ca. 2000.
  • Beispiel 4 Phosphcrsäureester eines butoxylierten 1,4-Buiandiols.
  • Beispiel 5 Phosphorsäureester eines äthoxylierten und höher propoxylierten Äthylenglykols.
  • Beispiel 6 Phosphorsäureester eines äthoxylierten u. propoxylierten Äthylenglykols.
  • Beispiel 8 Phosphorsäureester eines äthoxylierten und propoxylierten und butoxylierten Äthylenglykols
  • Beispiel 9 Phosphorsäureester eines äthoxylierten und propoxylierten Trimethylolpropans.
  • Beispiel 10 Phosphorsäureester eines äthoxylierten und propoxylierten Äthvlendiamins.
The test results are listed in the attached table. The triethanolamine salts of the phosphoric acid esters investigated were compared in each case. The ratio of ester: triethanolamine was adjusted so that a pH in the range from 8.3 to 8.8 results in the dilute aqueous solutions. The concentrations given relate to the salt in the Herberts test and in the gray cast iron test. In the foam test, 2 g / l were used, the calculation being based on the phosphoric acid ester contained. The abrasion area in mm 2 on the Reichert friction wear machine was measured in 1 s solution in water of 10 ° d hardness, the concentration relating to the phosphoric acid ester contained. The following phosphoric acid esters were compared:
  • Comparison I commercial product (phosphoric acid ester of an ethoxylated, substituted aromatic).
  • Comparison II commercial product (phosphoric acid ester of a substituted aromatic which is reacted with various alkylene oxides).
  • Comparison III commercial producer (phosphoric acid ester of a short-chain fatty alcohol with a predominant amount of moncester).
  • Comparison IV commercial product (phosphoric acid ester of an ethoxylated and propoxylated fatty alcohol).
  • Example 1 Phosphoric acid ester of a polypropylene glycol with a molecular weight of approximately 2230.
  • Example 2 Phosphoric acid esters of polypropylene glycol with a molecular weight of approximately 2000.
  • Example 4 Phosphorous Acid Ester of a Butoxylated 1,4-Buianediol.
  • Example 5 Phosphoric acid ester of an ethoxylated and higher propoxylated ethylene glycol.
  • Example 6 phosphoric acid ester of an ethoxylated u. propoxylated ethylene glycol.
  • Example 8 Phosphoric acid esters of an ethoxylated and propoxylated and butoxylated ethylene glycol
  • Example 9 Phosphoric acid ester of an ethoxylated and propoxylated trimethylol propane.
  • Example 10 Phosphoric acid esters of an ethoxylated and propoxylated ethylenediamine.

Die jeweils notwendigen Mischungsverhältnisse für das Tri- äthanolaminsalz sind in der Tabelle aufgeführt. Hierbei handelt es sich um Gewichtsverhälthisse.The mixing ratios required for the triethanolamine salt are listed in the table. These are weight ratios.

Die Tabellenergebnisse zeigen, daß die erfindungsgemäß zu verwendenden Produkte hinsichtlich ihrer antikorro- siven Wirkung den bisherigen Produkten nahezu gleichkommen. Gleichzeiting zeigt sich aber, daß sie bedeutend schaumärmer sind. Die Schaumwerte (Schaumvolumen nach 1 Minute) geben zwar nur Hinweise, die allgemeine Tendenz ist aber deutlioh erkennbar.The results of the table show that the products to be used according to the invention are almost equivalent to the previous products in terms of their anticorrosive effect. At the same time, however, it turns out that they are significantly less foaming. The foam values (foam volume after 1 minute) only give indications, but the general tendency is clearly recognizable.

Außerdem zeigt sich eine gute Schmierwirkung, wobei die Werte des Reibverschleistestes ebenfalls nur die Tendenz wiedergeben.In addition, there is a good lubricating effect, the values of the friction wear test also only reflect the tendency.

Mit den Produkten ist somit eine optimale Kompremißlösung gefunden worden - in den meisten Anwendungsfällen sind jetzt keine zusätzlichen Additive (Entsohäumer oder Sehmieradditive) mehr nötig.An optimal compromise solution has thus been found with the products - in most applications, no additional additives (demineralizers or Sehmier additives) are now necessary.

Figure imgb0004
Figure imgb0004
Figure imgb0005
Figure imgb0005

Claims (2)

1. Verwendung von sauren Phcsphcrsäureestern aus Phosphorsäuren und aliphatischen Diolen, Triolen oder Tetrolen mit 2 bis 8 C-Atcmen, die mit Propylenoxid und/oder Butylenoxid alkoxyliert sind und wobei die Alkylenoxidanteile zusammen Molekulargewichte von 200 bis 8.000 besitzen, oder deren Salze als schaumarme Korrosionsschutz- und Schmiermittel für Metalle.1. Use of acidic phosphate esters from phosphoric acids and aliphatic diols, triols or tetrols with 2 to 8 carbon atoms, which are alkoxylated with propylene oxide and / or butylene oxide and where the alkylene oxide portions together have molecular weights of 200 to 8,000, or their salts as low-foam corrosion protection - and lubricants for metals. 2. Verwendung nach Anspruch 1 von Dielen, Triolen oder Tetrclen, die zusätzlich noch Äthylenddoxideinheiten enthalten.2. Use according to claim 1 of floorboards, triplets or tetrclen, which additionally contain ethylenedioxide units.
EP78101697A 1977-12-20 1978-12-15 Use of acid esters of phosphoric acids and alkoxylated aliphatic polyols as corrosion inhibitors and lubricants Expired EP0002530B1 (en)

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Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0028674A1 (en) * 1979-10-12 1981-05-20 Hoechst Aktiengesellschaft Use of acidic phosphoric acid esters or their salts as corrosion inhibitors for metals
EP0134699A1 (en) * 1983-08-06 1985-03-20 The British Petroleum Company p.l.c. Surface treatment of metal
US4610222A (en) * 1984-07-23 1986-09-09 Union Carbide Corporation Cooling system using an oil-in-alcohol containing consolute antifreeze composition
US4613445A (en) * 1984-07-23 1986-09-23 Union Carbide Corporation Organophosphate-containing antifreeze
US4684474A (en) * 1984-07-23 1987-08-04 First Brands Corporation Organophosphate-containing antifreeze with buffer
US4684475A (en) * 1984-07-23 1987-08-04 First Brands Corporation Organophosphate and silicate containing antifreeze
EP0454110A1 (en) * 1990-04-26 1991-10-30 Hoechst Aktiengesellschaft Fluids based on glycol compounds, for metal corrosion inhibiting brakes
US5073283A (en) * 1984-07-23 1991-12-17 First Brands Corporation Antifreeze composition concentrate containing oxyalkylene compound and an organic phosphate surface modifier compound
EP0567212A1 (en) * 1992-04-21 1993-10-27 Petrolite Corporation The reaction product of nitrogen bases and phosphate esters as corrosion inhibitors
US20120164474A1 (en) * 2008-12-04 2012-06-28 Basf Se Method for producing molded bodies from sheet steel galvanized on one or both sides
CN115138106A (en) * 2022-08-03 2022-10-04 合肥新万成环保科技有限公司 High-carbon alcohol defoaming agent for high-temperature universal papermaking white water and preparation method thereof

Families Citing this family (2)

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WO1986000918A1 (en) * 1984-07-23 1986-02-13 Union Carbide Corporation Pseudo oil-containing antifreeze
FR3045066B1 (en) 2015-12-14 2017-12-08 Rhodia Operations ALCOXYLATED PHOSPHATE ESTERS FOR LUBRICATING COMPOSITIONS

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US2904416A (en) * 1957-10-30 1959-09-15 Exxon Research Engineering Co Petroleum distillate fuels
US2995532A (en) * 1958-11-20 1961-08-08 Gulf Oil Corp Corrosion preventive composition
FR1401507A (en) * 1963-05-17 1965-06-04 Lubrizol Corp Process for the production of esters containing phosphorus
US3215715A (en) * 1961-09-22 1965-11-02 Lubrizol Corp Metal-containing phosphate complexes and method of preparing same
FR1535198A (en) * 1966-08-31 1968-08-02 Rohm & Haas Dispersant and anti-corrosive compositions
DE1521720A1 (en) * 1964-07-04 1969-09-18 Degussa Process for inhibiting corrosion
GB1218276A (en) * 1968-08-19 1971-01-06 Nalco Chemical Co Scale and corrosion inhibition

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US2425845A (en) * 1945-04-21 1947-08-19 Carbide & Carbon Chem Corp Mixtures of polyoxyalkylene diols and methods of making such mixtures
US2904416A (en) * 1957-10-30 1959-09-15 Exxon Research Engineering Co Petroleum distillate fuels
US2995532A (en) * 1958-11-20 1961-08-08 Gulf Oil Corp Corrosion preventive composition
US3215715A (en) * 1961-09-22 1965-11-02 Lubrizol Corp Metal-containing phosphate complexes and method of preparing same
FR1401507A (en) * 1963-05-17 1965-06-04 Lubrizol Corp Process for the production of esters containing phosphorus
DE1521720A1 (en) * 1964-07-04 1969-09-18 Degussa Process for inhibiting corrosion
FR1535198A (en) * 1966-08-31 1968-08-02 Rohm & Haas Dispersant and anti-corrosive compositions
GB1218276A (en) * 1968-08-19 1971-01-06 Nalco Chemical Co Scale and corrosion inhibition

Cited By (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0028674A1 (en) * 1979-10-12 1981-05-20 Hoechst Aktiengesellschaft Use of acidic phosphoric acid esters or their salts as corrosion inhibitors for metals
EP0134699A1 (en) * 1983-08-06 1985-03-20 The British Petroleum Company p.l.c. Surface treatment of metal
US5073283A (en) * 1984-07-23 1991-12-17 First Brands Corporation Antifreeze composition concentrate containing oxyalkylene compound and an organic phosphate surface modifier compound
US4610222A (en) * 1984-07-23 1986-09-09 Union Carbide Corporation Cooling system using an oil-in-alcohol containing consolute antifreeze composition
US4613445A (en) * 1984-07-23 1986-09-23 Union Carbide Corporation Organophosphate-containing antifreeze
US4684474A (en) * 1984-07-23 1987-08-04 First Brands Corporation Organophosphate-containing antifreeze with buffer
US4684475A (en) * 1984-07-23 1987-08-04 First Brands Corporation Organophosphate and silicate containing antifreeze
EP0454110A1 (en) * 1990-04-26 1991-10-30 Hoechst Aktiengesellschaft Fluids based on glycol compounds, for metal corrosion inhibiting brakes
EP0567212A1 (en) * 1992-04-21 1993-10-27 Petrolite Corporation The reaction product of nitrogen bases and phosphate esters as corrosion inhibitors
USRE36291E (en) * 1992-04-21 1999-09-07 Baker Hughes Incorporated Reaction product of nitrogen bases and phosphate esters as corrosion inhibitors
US20120164474A1 (en) * 2008-12-04 2012-06-28 Basf Se Method for producing molded bodies from sheet steel galvanized on one or both sides
US9228148B2 (en) * 2008-12-04 2016-01-05 Voestalpine Stahl Gmbh Method for producing molded bodies from sheet steel galvanized on one or both sides
CN115138106A (en) * 2022-08-03 2022-10-04 合肥新万成环保科技有限公司 High-carbon alcohol defoaming agent for high-temperature universal papermaking white water and preparation method thereof
CN115138106B (en) * 2022-08-03 2024-04-23 合肥新万成环保科技有限公司 High-temperature general high-carbon alcohol defoamer for papermaking white water and preparation method thereof

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DE2756747A1 (en) 1979-06-28
DE2860449D1 (en) 1981-02-26

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