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EP0605839A1 - Cooling lubricants containing partially neutralised phosphoric acid esters as extreme-pressure additives - Google Patents

Cooling lubricants containing partially neutralised phosphoric acid esters as extreme-pressure additives Download PDF

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Publication number
EP0605839A1
EP0605839A1 EP93120595A EP93120595A EP0605839A1 EP 0605839 A1 EP0605839 A1 EP 0605839A1 EP 93120595 A EP93120595 A EP 93120595A EP 93120595 A EP93120595 A EP 93120595A EP 0605839 A1 EP0605839 A1 EP 0605839A1
Authority
EP
European Patent Office
Prior art keywords
phosphoric acid
group
extreme
acid esters
additive
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.)
Withdrawn
Application number
EP93120595A
Other languages
German (de)
French (fr)
Inventor
Peter Pyka
Franz Rehberger
Guido Dr. Scholz
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Hoechst AG
Original Assignee
Hoechst AG
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Hoechst AG filed Critical Hoechst AG
Publication of EP0605839A1 publication Critical patent/EP0605839A1/en
Withdrawn legal-status Critical Current

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Classifications

    • 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
    • C10M137/06—Metal salts
    • 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
    • C10M173/00—Lubricating compositions containing more than 10% water
    • 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
    • C10M2201/00—Inorganic compounds or elements as ingredients in lubricant compositions
    • C10M2201/02—Water
    • 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
    • C10M2223/00—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
    • C10M2223/02—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having no phosphorus-to-carbon bonds
    • C10M2223/04—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
    • C10M2223/00—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
    • C10M2223/02—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having no phosphorus-to-carbon bonds
    • C10M2223/04—Phosphate esters
    • C10M2223/041—Triaryl phosphates
    • 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
    • C10M2223/00—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
    • C10M2223/02—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having no phosphorus-to-carbon bonds
    • C10M2223/04—Phosphate esters
    • C10M2223/042—Metal salts thereof
    • 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
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/20—Metal working
    • C10N2040/22—Metal working with essential removal of material, e.g. cutting, grinding or drilling
    • 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
    • C10N2050/00—Form in which the lubricant is applied to the material being lubricated
    • C10N2050/01—Emulsions, colloids, or micelles

Definitions

  • the present invention relates to the use of partially neutralized Phosphorklaestern as EP-additives (E Xtreme P ressure additives) in cooling lubricants.
  • Cooling lubricants are used in both metal-cutting and non-cutting processing of metallic materials. Cooling lubricants have the task of dissipating heat and reducing process-related frictional forces.
  • a cooling lubricant is based on a water-in-oil emulsion.
  • the cooling lubricant concentrate contains emulsifiers, biocides, defoamers, corrosion inhibitors, EP additives, mineral oil and / or synthetic oils.
  • a usable emulsion is obtained by dilution with water. the usual use concentration is in the range of 1 to 20% (m / m).
  • EP additives contain chlorine, sulfur or / and phosphorus compounds or combinations which themselves or their thermal breakdown products form reaction layers which can be sheared off with the surfaces of the metals.
  • These highly adhesive, easily shearable reaction layers consist of the metal salts of the additives used. The reaction layers formed are effective until they are melted by an increase in temperature as a result of frictional heat.
  • Chlorine-containing additives work in a temperature range of approx. 180 ° C to 670 ° C
  • phosphorus-containing additives are assigned a temperature range of approx. 240 ° C to 900 ° C.
  • Sulfur additives cover the upper temperature range from approx. 530 ° C to over From 1000 ° C.
  • the invention thus relates to the use of alkali or alkaline earth metal salts of compounds of the formula wherein R1 represents a hydrogen atom or a C1-C20 alkyl group, a C2-C20 alkenyl group or an optionally substituted C6-C10 aryl group and R2 represents a C1-C20 alkyl group, a C2-C20 alkenyl group or an optionally substituted C6-C10 -Aryl group means.
  • Alkali or alkaline earth metal salts used are those of compounds of the formula wherein R1 is a hydrogen atom or a C1-C20-, preferably C1-C6-alkyl group, a C2-C20-, preferably C2-C6-alkenyl group or an optionally substituted C6-C10-, preferably C6-aryl group and R2 is a C1-C20 -, preferably C1-C6-alkyl group, a C2-C20-, preferably C2-C6-alkenyl group or an optionally substituted C6-C10-, preferably C6-aryl group.
  • the phosphoric acid ester is initially introduced and the aqueous alkali or alkaline earth compound, preferably the hydroxide (if possible concentrated), is slowly added with stirring.
  • the heat of neutralization generated is dissipated by cooling.
  • the cooling lubricant according to the invention contains 5 to 50%, based on the ester, emulsifiers, corrosion inhibitor, mineral oil and / or synthetic oil, bactericide and defoamer, the following quantitative ratios being present: Phosphorus compound 5 to 50% Emulsifier 10 to 50% Anticorrosive 5 to 30% mineral oil 5 to 20% Synthetic oil 5 to 20% Bactericide 0.5 to 2% Defoamer 0.01 to 0.5%, where the sum of all components is 100%.
  • Emulsifiers reduce the surface tension of the oil droplets floating in the water.
  • Suitable emulsifiers are ionic emulsifiers, for example amine soaps, alkali soaps, sulfonates, nonionic emulsifiers, for example ethoxylated longer-chain alcohols.
  • Suitable corrosion inhibitors are, for example, alkali or alkanolamine salts of organic acids, amines, sulfonates.
  • Biocides are used to keep the microbiological infestation of an emulsion with bacteria, fungi and yeast as low as possible.
  • Defoamers are used to suppress the tendency of the emulsion to foam, for example silicone oils are suitable.
  • Suitable mineral oils are paraffinic or naphthenic oils of the different viscosity classes.
  • polyethylene glycols for example, polyethylene glycols, mixed polyglycols, polyolefins or carboxylic acid esters are used as synthetic oils.
  • the phosphoric acid ester was characterized by the following key figures: Phosphorus content approx. 18.8% (m / m) Density at 20 ° C 1.2 g / cm3 Viscosity at 20 ° C 430 mPa.s Viscosity at 40 ° C 136 mm2 / s Acid number approx. 490 mg KOH / g pH at 20 ° C 1.6
  • the test specimens consist of a slip ring (ball bearing ring) and a roller body (for rolling bearings). During the test, the roller body is crossed axially and pressed onto the slip ring with a 150 N or 300 N double lever system.
  • a third of the slip ring is immersed in the test liquid and brings enough lubricant to the friction point at 900 rpm.
  • the slip ring runs 100 m.
  • the wear path is noted as the number of meters at which the grinding noise disappears (noise meter).
  • the elliptical ground mark obtained by the friction at the point of contact (slip ring roller body) is measured with a measuring magnifier.
  • the surface area of the cut mark serves as a direct criterion for wear and the specific surface pressure as a measure of the compressive strength of lubricants.
  • Three test runs are carried out to determine the specific surface pressure; a cleaning run must be carried out after each test run. An average is formed from the three cut marks obtained. The noise meters and the specific surface pressure are used to assess the lubricant.
  • the cutting tests were carried out at cutting speeds of 50 m / min, 60 m / min and 85 m / min.
  • the depth of cut was 1.0 mm at a feed rate of 0.1 mm / revolution.
  • the free area wear on the turning tool was measured after 5 min.
  • the attempt was made after reaching one Free space wear of 0.2 mm canceled.
  • a steel with the designation C 100 W 1 (medium hard to cut) with the following composition was used as material: carbon 1.0% silicon 0.17% manganese 0.17% sulfur 0.02%
  • a cutting agent containing phosphoric acid ester according to recipe 1 (10% in drinking water) was used in the machining tests.
  • a cooling lubricant according to recipe 2 (10% in drinking water) and a chlorine-containing cooling lubricant on the market (10% in drinking water) served as a comparison.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Chemistry (AREA)
  • Lubricants (AREA)

Abstract

A cooling lubricant which contains, as an extreme-pressure additive, an alkali metal salt or alkaline earth metal salt of a compound of the formula <IMAGE> is distinguished by an improved additive effect as compared with products which contain amine salts. It is free of diethanolamine and can therefore not form any nitrosamine in use.

Description

Die vorliegende Erfindung bezieht sich auf den Einsatz von teilneutralisierten Phosphorsäureestern als EP-Additive (Extreme-Pressure Additive) in Kühlschmierstoffen.The present invention relates to the use of partially neutralized Phosphorsäureestern as EP-additives (E Xtreme P ressure additives) in cooling lubricants.

Kühlschmierstoffe werden sowohl bei der spanabhebenden, als auch bei der spanlosen Bearbeitung von metallischen Werkstoffen eingesetzt. Dabei haben Kühlschmierstoffe die Aufgabe, entstehende Wärme abzuführen und prozeßbedingte Reibungskräfte zu verringern.Cooling lubricants are used in both metal-cutting and non-cutting processing of metallic materials. Cooling lubricants have the task of dissipating heat and reducing process-related frictional forces.

Ein Kühlschmierstoff ist auf einer Wasser-in-Öl-Emulsion aufgebaut. Das Kühlschmierstoffkonzentrat enthält Emulgatoren, Biozide, Entschäumer, Korrosionsinhibitoren, EP-Additive, Mineralöl und/oder Syntheseöle. Durch Verdünnen mit Wasser erhält man eine gebrauchsfähige Emulsion. die übliche Einsatzkonzentration liegt im Bereich von 1 bis 20 % (m/m).A cooling lubricant is based on a water-in-oil emulsion. The cooling lubricant concentrate contains emulsifiers, biocides, defoamers, corrosion inhibitors, EP additives, mineral oil and / or synthetic oils. A usable emulsion is obtained by dilution with water. the usual use concentration is in the range of 1 to 20% (m / m).

EP-Additive enthalten Chlor-, Schwefel- oder/und Phosphorverbindungen bzw. Kombinationen, die selbst oder deren thermische Spaltprodukte mit den Oberflächen der Metalle abscherbare Reaktionsschichten bilden. Diese gut haftenden leicht scherbaren Reaktionsschichten bestehen aus den Metallsalzen der eingesetzten Additive. Die gebildeten Reaktionsschichten sind solange wirksam, bis sie durch Temperaturerhöhung infolge Reibungswärme aufgeschmolzen werden.EP additives contain chlorine, sulfur or / and phosphorus compounds or combinations which themselves or their thermal breakdown products form reaction layers which can be sheared off with the surfaces of the metals. These highly adhesive, easily shearable reaction layers consist of the metal salts of the additives used. The reaction layers formed are effective until they are melted by an increase in temperature as a result of frictional heat.

Die Reaktivität dieser Additive ist temperaturabhängig. Chlorhaltige Additive wirken in einem Temperaturbereich von ca. 180°C bis 670°C, phosphorhaltigen Additiven wird ein Temperaturbereich von ca. 240°C bis 900°C zugeordnet. Schwefeladditive decken den oberen Temperaturbereich von ca. 530°C bis über 1000°C ab.The reactivity of these additives depends on the temperature. Chlorine-containing additives work in a temperature range of approx. 180 ° C to 670 ° C, phosphorus-containing additives are assigned a temperature range of approx. 240 ° C to 900 ° C. Sulfur additives cover the upper temperature range from approx. 530 ° C to over From 1000 ° C.

Der Einsatz von Phosphorsäureestern als Schmierstoffzusatz für die Kaltumformung von Metallen ist bekannt (vgl. EP 146 140).The use of phosphoric acid esters as a lubricant additive for the cold forming of metals is known (cf. EP 146 140).

Bekannt ist auch der Einsatz von öllöslichen Salzen von Aminen mit schwachen Säuren als EP-Zusätze (vgl. EP 391 653), unter anderem werden hier auch Phosphorsäureester genannt. Allerdings enthält das bei der Neutralisation von Phosphorsäureestern zur Anwendung kommende Triethanolamin (technisch) auch das in der Metallindustrie unerwünschte Diethanolamin, welches zur Nitrosaminbildung neigt.It is also known to use oil-soluble salts of amines with weak acids as EP additives (cf. EP 391 653), including phosphoric acid esters. However, the triethanolamine used (technically) in the neutralization of phosphoric acid esters also contains the diethanolamine which is undesirable in the metal industry and tends to form nitrosamine.

Es wurde gefunden, daß Gemische aus Mono- und Diestern der Phosphorsäuren, neutralisiert mit wäßrigem Alkali anstelle von Triethanolamin, für den Einsatz in Kühlschmierstoffen besonders gute Ergebnisse liefern.It has been found that mixtures of mono- and diesters of phosphoric acids, neutralized with aqueous alkali instead of triethanolamine, give particularly good results for use in cooling lubricants.

Die Erfindung betrifft somit die Verwendung von Alkali- oder Erdalkalisalzen von Verbindungen der Formel

Figure imgb0001

worin R¹ ein Wasserstoffatom oder eine C₁-C₂₀-Alkylgruppe, eine C₂-C₂₀-Alkenylgruppe oder eine gegebenenfalls substituierte C₆-C₁₀-Arylgruppe bedeutet und R² eine C₁-C₂₀-Alkylgruppe, eine C₂-C₂₀-Alkenylgruppe oder eine gegebenenfalls substituierte C₆-C₁₀-Arylgruppe bedeutet.The invention thus relates to the use of alkali or alkaline earth metal salts of compounds of the formula
Figure imgb0001
wherein R¹ represents a hydrogen atom or a C₁-C₂₀ alkyl group, a C₂-C₂₀ alkenyl group or an optionally substituted C₆-C₁₀ aryl group and R² represents a C₁-C₂₀ alkyl group, a C₂-C₂₀ alkenyl group or an optionally substituted C₆-C₁₀ -Aryl group means.

Zur Anwendung kommende Alkali- oder Erdalkalisalze sind solche von Verbindungen der Formel

Figure imgb0002

worin R¹ ein Wasserstoffatom oder eine C₁-C₂₀-, vorzugsweise C₁-C₆-Alkylgruppe, eine C₂-C₂₀-, vorzugsweise C₂-C₆-Alkenylgruppe oder eine gegebenenfalls substituierte C₆-C₁₀-, vorzugsweise C₆-Arylgruppe bedeutet und R² eine C₁-C₂₀-, vorzugsweise C₁-C₆-Alkylgruppe, eine C₂-C₂₀-, vorzugsweise C₂-C₆-Alkenylgruppe oder eine gegebenenfalls substituierte C₆-C₁₀-, vorzugsweise C₆-Arylgruppe bedeutet.Alkali or alkaline earth metal salts used are those of compounds of the formula
Figure imgb0002
wherein R¹ is a hydrogen atom or a C₁-C₂₀-, preferably C₁-C₆-alkyl group, a C₂-C₂₀-, preferably C₂-C₆-alkenyl group or an optionally substituted C₆-C₁₀-, preferably C₆-aryl group and R² is a C₁-C₂₀ -, preferably C₁-C₆-alkyl group, a C₂-C₂₀-, preferably C₂-C₆-alkenyl group or an optionally substituted C₆-C₁₀-, preferably C₆-aryl group.

Zur Neutralisation wird der Phosphorsäureester vorgelegt und die wäßrige Alkali- oder Erdalkaliverbindung, bevorzugt das Hydroxid (möglichst konzentriert), wird langsam unter Rühren zugegeben. Die dabei entstehende Neutralisationswärme wird durch Kühlung abgeführt.For neutralization, the phosphoric acid ester is initially introduced and the aqueous alkali or alkaline earth compound, preferably the hydroxide (if possible concentrated), is slowly added with stirring. The heat of neutralization generated is dissipated by cooling.

Es hat sich als günstig erwiesen, die Phosphorsäureester bis zum ersten Umschlagepunkt (zu bestimmen mittels potentiometrischer Titration) zu neutralisieren.It has proven advantageous to neutralize the phosphoric acid esters up to the first transition point (to be determined using potentiometric titration).

Der erfindungsgemäße Kühlschmierstoff enthält neben dem teilneutralisierten Phosphorsäureester 5 bis 50 %, bezogen auf den Ester, Emulgatoren, Korrosionsschutzmittel, Mineralöl und/oder synthetisches Öl, Bakterizid und Entschäumer, wobei folgende Mengenverhältnisse vorliegen: Phosphorverbindung 5 bis 50 % Emulgator 10 bis 50 % Korrosionsschutzmittel 5 bis 30 % Mineralöl 5 bis 20 % Synthetisches Öl 5 bis 20 % Bakterizid 0,5 bis 2 % Entschäumer 0,01 bis 0,5 %,
wobei die Summe aller Bestandteile 100 % beträgt.In addition to the partially neutralized phosphoric acid ester, the cooling lubricant according to the invention contains 5 to 50%, based on the ester, emulsifiers, corrosion inhibitor, mineral oil and / or synthetic oil, bactericide and defoamer, the following quantitative ratios being present: Phosphorus compound 5 to 50% Emulsifier 10 to 50% Anticorrosive 5 to 30% mineral oil 5 to 20% Synthetic oil 5 to 20% Bactericide 0.5 to 2% Defoamer 0.01 to 0.5%,
where the sum of all components is 100%.

Durch Verdünnen des Kühlschmierstoffes mit Wasser erhält man eine Öl-in-Wasser-Emulsion, Wasser-in-Öl-Emulsion oder eine Kühlschmierstofflösung.By diluting the cooling lubricant with water, an oil-in-water emulsion, water-in-oil emulsion or a cooling lubricant solution is obtained.

Emulgatoren verringern die Oberflächenspannung der im Wasser schwebenden Öltröpfchen. Geeignete Emulgatoren sind ionische Emulgatoren, beispielsweise Aminseifen, Alkaliseifen, Sulfonate, nichtionische Emulgatoren, beispielsweise ethoxilierte längerkettige Alkohole.Emulsifiers reduce the surface tension of the oil droplets floating in the water. Suitable emulsifiers are ionic emulsifiers, for example amine soaps, alkali soaps, sulfonates, nonionic emulsifiers, for example ethoxylated longer-chain alcohols.

Geeignete Korrosionsinhibitoren sind beispielsweise Alkali- oder Alkanolaminsalze von organischen Säuren, Aminen, Sulfonaten.Suitable corrosion inhibitors are, for example, alkali or alkanolamine salts of organic acids, amines, sulfonates.

Biozide werden eingesetzt, um den mikrobiologischen Befall einer Emulsion durch Bakterien, Pilzen und Hefen möglichst niedrig zu halten.Biocides are used to keep the microbiological infestation of an emulsion with bacteria, fungi and yeast as low as possible.

Entschäumer werden eingesetzt, um die Schaumneigung der Emulsion zurückzudrängen, geeignet sind beispielsweise Silikonöle.Defoamers are used to suppress the tendency of the emulsion to foam, for example silicone oils are suitable.

Geeignete Mineralöle sind paraffinische oder naphthenische Öle der verschiedenen Viskositätsklassen.Suitable mineral oils are paraffinic or naphthenic oils of the different viscosity classes.

Als synthetische Öle werden beispielsweise Polyethylenglykole, Mischpolyglykole, Polyolefine oder Carbonsäureester eingesetzt.For example, polyethylene glycols, mixed polyglycols, polyolefins or carboxylic acid esters are used as synthetic oils.

Der erfindungsgemäße Kühlschmierstoff bietet folgende Vorteile:

  • Eine bessere Additivwirkung als aminneutralisierte Phosphorverbindungen enthaltende Produkte.
  • Er ist frei von Triethanolamin (Diethanolamin), dadurch keine Nitrosaminbildung während des Einsatzes.
The cooling lubricant according to the invention offers the following advantages:
  • A better additive effect than products containing amine neutralized phosphorus compounds.
  • It is free of triethanolamine (diethanolamine), so there is no formation of nitrosamine during use.

Beispielexample

Für die nachfolgenden Versuche wurde ein Gemisch herangezogen, welches aus 44 % Phosphorsäuremono- und 53 % Phosphorsäurediisopropylester (Rest freier Alkohol/freie Säure) bestand.
Dieser Phosphorsäureester ist im Handel unter der Bezeichnung Phosphorsäureester MDIP erhältlich (HOECHST AG).For the subsequent experiments, a mixture was used which consisted of 44% phosphoric acid mono- and 53% phosphoric acid diisopropyl ester (rest free alcohol / free acid).
This phosphoric acid ester is commercially available under the name phosphoric acid ester MDIP (HOECHST AG).

Der Phosphorsäureester war durch folgende Kennzahlen charakterisiert: Phosphorgehalt ca. 18,8 % (m/m) Dichte bei 20°C 1,2 g/cm³ Viskosität bei 20°C 430 mPa.s Viskosität bei 40°C 136 mm²/s Säurezahl ca. 490 mg KOH/g pH-Wert bei 20°C 1,6 The phosphoric acid ester was characterized by the following key figures: Phosphorus content approx. 18.8% (m / m) Density at 20 ° C 1.2 g / cm³ Viscosity at 20 ° C 430 mPa.s Viscosity at 40 ° C 136 mm² / s Acid number approx. 490 mg KOH / g pH at 20 ° C 1.6

Ergebnisse der potentiometrischen Titration:

  • 1. Umschlagepunkt bei pH 7,15
  • 2. Umschlagepunkt bei pH 11,9
Zur Neutralisation wurden 15 g des vorstehend bezeichneten Phosphorsäureesters vorgelegt und langsam mit 20 cm³ 40 %iger KOH versetzt. Es resultierte ein pH-Wert von 8,5. Dieser teilneutralisierte Ester wurde in dem nachstehenden Rezept 1 auf seine Eignung als EP-Additiv geprüft:Results of the potentiometric titration:
  • 1st transition point at pH 7.15
  • 2nd transition point at pH 11.9
For neutralization, 15 g of the above-mentioned phosphoric acid ester were introduced and 20 cm 3 of 40% KOH were slowly added. The result was a pH of 8.5. This partially neutralized ester was tested in recipe 1 below for its suitability as an EP additive:

Rezept 1Recipe 1

35,00 % mit KOH teilneutralisierter Phosphorsäureester
35,00 % anionische/nichtionische Emulgatoren
15,00 % Korrosionsinhibitor
13,00 % Mineralöl
1,99 % Bakterizid
0,01 % Entschäumer
Zum Vergleich wurde der gleiche Phosphorsäureester mit Triethanolamin teilneutralisiert und in einem ansonsten identischen Rezept geprüft.35.00% phosphoric acid ester partially neutralized with KOH
35.00% anionic / nonionic emulsifiers
15.00% corrosion inhibitor
13.00% mineral oil
1.99% bactericide
0.01% defoamer
For comparison, the same phosphoric acid ester was partially neutralized with triethanolamine and tested in an otherwise identical recipe.

Rezept 2Recipe 2

35,00 % mit Triethanolamin teilneutralisierter Phosphorsäureester
35,00 % anionische/nichtionische Emulgatoren
15,00 % Korrosionsinhibitor
13,00 % Mineralöl
1,99 % Bakterizid
0,01 % Entschäumer35.00% phosphoric acid ester partially neutralized with triethanolamine
35.00% anionic / nonionic emulsifiers
15.00% corrosion inhibitor
13.00% mineral oil
1.99% bactericide
0.01% defoamer

1. Ergebnis auf der Reibverschleißwaage nach Reichert1. Result on the friction wear scale according to Reichert

Die Prüfkörper bestehen aus einem Schleifring (Kugellagerring) und einem Walzenkörper (für Wälzlager). Bei der Prüfung wird der Walzenkörper axial gekreuzt und über ein Doppelhebelsystem mit 150 N oder 300 N auf den Schleifring gepreßt.The test specimens consist of a slip ring (ball bearing ring) and a roller body (for rolling bearings). During the test, the roller body is crossed axially and pressed onto the slip ring with a 150 N or 300 N double lever system.

Der Schleifring taucht zu einem Drittel in die Prüfflüssigkeit ein und bringt mit 900 U/min genügend Schmiermittel an die Reibstelle. Der Laufweg des Schleifringes beträgt 100 m. Der Verschleißweg wird als die Meterzahl notiert, bei der das Schleifgeräusch verschwindet (Geräuschmeter). Die durch die Reibung an der Berührungsstelle (Schleifring-Walzenkörper) erhaltene ellipsenförmig ausgebildete Schliffmarke wird mit einer Meßlupe ausgemessen.A third of the slip ring is immersed in the test liquid and brings enough lubricant to the friction point at 900 rpm. The slip ring runs 100 m. The wear path is noted as the number of meters at which the grinding noise disappears (noise meter). The elliptical ground mark obtained by the friction at the point of contact (slip ring roller body) is measured with a measuring magnifier.

Die Flächengröße der Schliffmarke dient als direktes Kriterium für den Verschleiß und die spezifische Flächenpressung als Maß für die Druckbelastbarkeit von Schmiermitteln. Für die Bestimmung der spezifischen Flächenpressung werden drei Prüfläufe durchgeführt, nach jedem Prüflauf muß ein Reinigungslauf erfolgen. Aus den drei erhaltenen Schliffmarken wird ein Mittelwert gebildet. Zur Beurteilung des Schmierstoffes werden die Geräuschmeter und die spezifischen Flächenpressung herangezogen.The surface area of the cut mark serves as a direct criterion for wear and the specific surface pressure as a measure of the compressive strength of lubricants. Three test runs are carried out to determine the specific surface pressure; a cleaning run must be carried out after each test run. An average is formed from the three cut marks obtained. The noise meters and the specific surface pressure are used to assess the lubricant.

Untersuchte ProdukteExamined products I. Marktgängiges Kühlschmierstoffkonzentrat mit folgenden KennzahlenI. Common cooling lubricant concentrate with the following key figures

Chlorgehalt (inaktiv)Chlorine content (inactive) 6 %6% Aktiver SchwefelActive sulfur 0 %0% MineralölgehaltMineral oil content 46 %46% WassergehaltWater content 5 %5%

II. Formulierung nach Rezept 1II. Formulation according to recipe 1 III. Formulierung nach Rezept 2III. Formulation according to recipe 2

Figure imgb0003
Figure imgb0003

2. Verschleißstandzeit-Drehversuche (Zerspanungsversuche) in Anlehnung an das Stahleisenprüfblatt 1162-692. Wear life turning tests (machining tests) based on steel iron test sheet 1162-69

Um die EP-Wirkung des teilneutralisierten Phosphorsäureesters in einem KSS zu prüfen, wurden Zerspanungsversuche in Anlehnung an Stahl-Eisen-Prüfblatt 1162-69 durchgeführt.To test the EP effect of the partially neutralized phosphoric acid ester in a KSS, machining tests were carried out based on steel-iron test sheet 1162-69.

Die Zerspanungsversuche wurden bei Schnittgeschwindigkeiten von 50 m/min, 60 m/min und 85 m/min durchgeführt. Die Spantiefe betrug 1,0 mm bei einem Vorschub von 0,1 mm/Umdrehung. Der Freiflächenverschleiß am Drehmeißel wurde nach je 5 min gemessen. Der Versuch wurde nach Erreichen eines Freiflächenverschleißes von 0,2 mm abgebrochen. Als Werkstoff wurde ein Stahl mit der Bezeichnung C 100 W 1 (mittelschwer zu zerspannen) mit folgender Zusammensetzung verwendet: Kohlenstoff 1,0 % Silizium 0,17 % Mangan 0,17 % Schwefel 0,02 % The cutting tests were carried out at cutting speeds of 50 m / min, 60 m / min and 85 m / min. The depth of cut was 1.0 mm at a feed rate of 0.1 mm / revolution. The free area wear on the turning tool was measured after 5 min. The attempt was made after reaching one Free space wear of 0.2 mm canceled. A steel with the designation C 100 W 1 (medium hard to cut) with the following composition was used as material: carbon 1.0% silicon 0.17% manganese 0.17% sulfur 0.02%

Bei den Zerspanungsversuchen wurde ein phosphorsäureesterhaltiger KSS nach Rezept 1 (10 %ig in Trinkwasser) eingesetzt. Als Vergleich darin diente ein KSS nach Rezept 2 (10 %ig in Trinkwasser) und ein chlorhaltiger marktgängier KSS (10 %ig in Trinkwasser).A cutting agent containing phosphoric acid ester according to recipe 1 (10% in drinking water) was used in the machining tests. A cooling lubricant according to recipe 2 (10% in drinking water) and a chlorine-containing cooling lubricant on the market (10% in drinking water) served as a comparison.

Die Prüfergebnisse sind aus der nachstehenden Tabelle zu ersehen.

Figure imgb0004
The test results are shown in the table below.
Figure imgb0004

Claims (3)

Verwendung von Alkali- oder Erdalkalisalzen von Verbindungen der Formel
Figure imgb0005
 worin R¹ ein Wasserstoffatom oder eine C₁-C₂₀-Alkylgruppe, eine C₂-C₂₀-Alkenylgruppe oder eine gegebenenfalls substituierte C₆-C₁₀-Arylgruppe bedeutet und R² eine C₁-C₂₀-Alkylgruppe, eine C₂-C₂₀-Alkenylgruppe oder eine gegebenenfalls substituierte C₆-C₁₀-Arylgruppe bedeutet, als EP-Additiv in Kühlschmierstoffen.Use of alkali or alkaline earth metal salts of compounds of the formula
Figure imgb0005
 wherein R¹ represents a hydrogen atom or a C₁-C₂₀ alkyl group, a C₂-C₂₀ alkenyl group or an optionally substituted C₆-C₁₀ aryl group and R² represents a C₁-C₂₀ alkyl group, a C₂-C₂₀ alkenyl group or an optionally substituted C₆-C₁₀ -Aryl group means as an EP additive in cooling lubricants. Kühlschmierstoff, enthaltend ein phosphorhaltiges EP-Additiv und 5 bis 50 %, bezogen auf die Phosphorverbindung, Emulgatoren, Korrosionsschutzmittel, Mineralöl und/oder synthetisches Öl, Bakterizid und Entschäumer, dadurch gekennzeichnet, daß das phosphorhaltige EP-Additiv ein Alkali- oder Erdalkalisalz einer Verbindung der Formel
Figure imgb0006
 worin R¹ ein Wasserstoffatom oder eine C₁-C₂₀-Alkylgruppe, eine C₂-C₂₀-Alkenylgruppe oder eine gegebenenfalls substituierte C₆-C₁₀-Arylgruppe bedeutet und R² eine C₁-C₂₀-Alkylgruppe, eine C₂-C₂₀-Alkenylgruppe oder eine gegebenenfalls substituierte C₆-C₁₀-Arylgruppe bedeutet, ist.Cooling lubricant containing a phosphorus-containing EP additive and 5 to 50%, based on the phosphorus compound, emulsifiers, anti-corrosion agents, mineral oil and / or synthetic oil, bactericide and defoamer, characterized in that the phosphorus-containing EP additive is an alkali or alkaline earth metal salt of a compound of the formula
Figure imgb0006
 wherein R¹ represents a hydrogen atom or a C₁-C₂₀ alkyl group, a C₂-C₂₀ alkenyl group or an optionally substituted C₆-C₁₀ aryl group and R² represents a C₁-C₂₀ alkyl group, a C₂-C₂₀ alkenyl group or an optionally substituted C₆-C₁₀ Aryl group means is. Kühlschmierstoff nach Anspruch 2, dadurch gekennzeichnet, daß das EP-Additiv ein Kaliumsalz einer Verbindung der Formel
Figure imgb0007
 worin R¹ ein Wasserstoffatom oder eine Isopropylgruppe und R² eine Isopropylgruppe bedeutet, ist.Cooling lubricant according to claim 2, characterized in that the EP additive is a potassium salt of a compound of the formula
Figure imgb0007
 wherein R¹ is a hydrogen atom or an isopropyl group and R² is an isopropyl group.
EP93120595A 1992-12-28 1993-12-21 Cooling lubricants containing partially neutralised phosphoric acid esters as extreme-pressure additives Withdrawn EP0605839A1 (en)

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Publication number Priority date Publication date Assignee Title
WO2000037591A1 (en) * 1998-12-23 2000-06-29 Rhodia Inc. Phosphate ester compositions in a weight ratio greater than 1:1 monoalkyl to dialkyl phosphate used as lubricant additives

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JP4528286B2 (en) * 2001-01-24 2010-08-18 新日本石油株式会社 Lubricating oil composition
JP3841687B2 (en) * 2001-01-24 2006-11-01 新日本石油株式会社 Lubricating oil composition

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Publication number Priority date Publication date Assignee Title
US2285854A (en) * 1934-02-23 1942-06-09 Du Pont Lubrication
US2328540A (en) * 1940-06-08 1943-09-07 Monsanto Chemicals Method of and material for treating metal
US2959549A (en) * 1956-11-23 1960-11-08 Exxon Research Engineering Co Water-base rust preventive and lubricant
GB2194782A (en) * 1985-11-09 1988-03-16 Ciba Geigy Ag Additives for aqueous functional fluids
WO1988003144A1 (en) * 1986-10-21 1988-05-05 The Lubrizol Corporation Oil-soluble metal salts of phosphoric acid esters

Patent Citations (5)

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Publication number Priority date Publication date Assignee Title
US2285854A (en) * 1934-02-23 1942-06-09 Du Pont Lubrication
US2328540A (en) * 1940-06-08 1943-09-07 Monsanto Chemicals Method of and material for treating metal
US2959549A (en) * 1956-11-23 1960-11-08 Exxon Research Engineering Co Water-base rust preventive and lubricant
GB2194782A (en) * 1985-11-09 1988-03-16 Ciba Geigy Ag Additives for aqueous functional fluids
WO1988003144A1 (en) * 1986-10-21 1988-05-05 The Lubrizol Corporation Oil-soluble metal salts of phosphoric acid esters

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DATABASE WPI Section Ch Week 7251, Derwent World Patents Index; Class E11, AN 72-80200T *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2000037591A1 (en) * 1998-12-23 2000-06-29 Rhodia Inc. Phosphate ester compositions in a weight ratio greater than 1:1 monoalkyl to dialkyl phosphate used as lubricant additives

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