DE1071870B - Mineral lubricating oils - Google Patents
Mineral lubricating oilsInfo
- Publication number
- DE1071870B DE1071870B DENDAT1071870D DE1071870DA DE1071870B DE 1071870 B DE1071870 B DE 1071870B DE NDAT1071870 D DENDAT1071870 D DE NDAT1071870D DE 1071870D A DE1071870D A DE 1071870DA DE 1071870 B DE1071870 B DE 1071870B
- Authority
- DE
- Germany
- Prior art keywords
- general formula
- lubricating oil
- mineral lubricating
- chlorinated
- compounds
- 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.)
- Pending
Links
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
- C10M1/00—Liquid compositions essentially based on mineral lubricating oils or fatty oils; Their use as lubricants
- C10M1/08—Liquid compositions essentially based on mineral lubricating oils or fatty oils; Their use as lubricants with additives
-
- 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
- C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
- C10M2207/02—Hydroxy compounds
- C10M2207/021—Hydroxy compounds having hydroxy groups bound to acyclic or cycloaliphatic carbon atoms
- C10M2207/022—Hydroxy compounds having hydroxy groups bound to acyclic or cycloaliphatic carbon atoms containing at least two hydroxy groups
-
- 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
- C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
- C10M2207/04—Ethers; Acetals; Ortho-esters; Ortho-carbonates
- C10M2207/046—Hydroxy ethers
-
- 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
- C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
- C10M2209/10—Macromolecular compoundss obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- C10M2209/103—Polyethers, i.e. containing di- or higher polyoxyalkylene groups
-
- 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
- C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
- C10M2209/10—Macromolecular compoundss obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- C10M2209/103—Polyethers, i.e. containing di- or higher polyoxyalkylene groups
- C10M2209/104—Polyethers, i.e. containing di- or higher polyoxyalkylene groups of alkylene oxides containing two carbon atoms only
-
- 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
- C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
- C10M2209/10—Macromolecular compoundss obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- C10M2209/103—Polyethers, i.e. containing di- or higher polyoxyalkylene groups
- C10M2209/108—Polyethers, i.e. containing di- or higher polyoxyalkylene groups etherified
-
- 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
- C10M2211/00—Organic non-macromolecular compounds containing halogen as ingredients in lubricant compositions
- C10M2211/02—Organic non-macromolecular compounds containing halogen as ingredients in lubricant compositions containing carbon, hydrogen and halogen only
-
- 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
- C10M2211/00—Organic non-macromolecular compounds containing halogen as ingredients in lubricant compositions
- C10M2211/02—Organic non-macromolecular compounds containing halogen as ingredients in lubricant compositions containing carbon, hydrogen and halogen only
- C10M2211/022—Organic non-macromolecular compounds containing halogen as ingredients in lubricant compositions containing carbon, hydrogen and halogen only aliphatic
-
- 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
- C10M2211/00—Organic non-macromolecular compounds containing halogen as ingredients in lubricant compositions
- C10M2211/06—Perfluorinated compounds
-
- 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
- C10M2211/00—Organic non-macromolecular compounds containing halogen as ingredients in lubricant compositions
- C10M2211/08—Halogenated waxes
Landscapes
- Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Lubricants (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
C I O M 169/00A30C I O M 169 / 00A30
deutsches /rnmm, PatentamtGerman / rnmm, Patent Office
kl. 23 c 1/01kl. 23 c 1/01
BEKANNTMACHUNG DER ANMELDUNG UND AUSGABE DER AÜSLEGESCHRIFT:NOTICE THE REGISTRATION AND ISSUE OF THE LEGAL LETTERING:
E 16681 IVc/23cE 16681 IVc / 23c
6. NOVEMBER 1958 24. DEZEMBER 1959NOVEMBER 6, 1958 DECEMBER 24, 1959
Chlorierte Kohlenwasserstoffe, insbesondere aliphatisohe Chlorkohlenwasserstoffe, finden als Hochdruckzusätze in Schmierölen Anwendung. Die Wirksamkeit der Chlorkohlenwasserstoffe ist weitgehend von ihrer Struktur abhängig: Die chlorierten aliphatischen Kohlenwasserstoffe sind erheblich wirksamer als chlorierte aromatische Kohlenwasserstoffe.Chlorinated hydrocarbons, especially aliphatic Chlorinated hydrocarbons are used as high pressure additives in lubricating oils. The effectiveness of chlorinated hydrocarbons is largely dependent on their structure: the chlorinated aliphatic Hydrocarbons are considerably more effective than chlorinated aromatic hydrocarbons.
Chlorparaffine zeigen im allgemeinen eine mehr oder weniger stark ausgeprägte Korrosivität gegenüber Metallen, namentlich Fe-Metallen; die Korrosivität kann in Gegenwart von Wasser so stark sein, daß die Anwendung von Chlorparaffinen als Hochdruckzusätze für Schmieröle nicht möglich ist.Chlorinated paraffins generally show a more or less pronounced corrosiveness towards them Metals, namely ferrous metals; the corrosiveness can be so strong in the presence of water that the use of chlorinated paraffins as high pressure additives for lubricating oils is not possible.
Chlorparaffine spalten, vornehmlich bei Temperaturen über 100° C, saure Produkte ab; die Unbeständigkeit nimmt mit steigender Temperatur zu. Es ist zwar bekannt, handelsübliche Chlorparaffine für den Einsatz bei verhältnismäßig niedriger Temperatur zu stabilisieren. Die Stabilisierung ist aber nicht ausreichend, wenn die Chlorparaffine auf höhere Tempe- ao ratur, z. B. 100° C und darüber, erhitzt werden; dann treten nämlich durch Anwesenheit minimaler Mengen an sauren Produkten, etwa Salzsäure, schwere Korrosionen an Fe-Metallen auf.Chlorinated paraffins split off acidic products, especially at temperatures above 100 ° C; the impermanence increases with increasing temperature. Although it is known to use commercially available chlorinated paraffins for the Use to stabilize at relatively low temperature. However, the stabilization is not sufficient, if the chlorinated paraffins to higher tempe- ao temperature, z. B. 100 ° C and above, are heated; then This is because the presence of minimal amounts of acidic products, such as hydrochloric acid, causes severe corrosion on Fe metals.
Die handelsüblichen Chlorparaffine haben je nach den Herstellungsverfahren und Ausgangsparaffinen voneinander abweichende Korrosionseigenschaften. Die praktische Erfahrung zeigt aber, daß in allen Fällen eine merkliche Aggressivität, insbesondere in Gegenwart von Wasser, gegenüber Fe-Metallen besteht. The commercially available chlorinated paraffins have, depending on the manufacturing process and starting paraffins different corrosion properties. However, practical experience shows that in all Cases a noticeable aggressiveness, especially in the presence of water, towards Fe-metals.
Theoretisch ist eine Neutralisierung und somit Unschädlichmachung der sauren Zersetzungsprodwkte von Chlorparaffinen verhältnismäßig einfach durch Zusatz öllöslicher Seifen zu erreichen. Diese Maßnähme ist aber nicht allgemein anwendbar, besonders dann nicht, wenn gleichzeitig die Forderung besteht, daß das Schmieröl nicht emulgieren darf. In solchen Fällen ist es unerläßlich, daß eine schnelle Trennung der Wasser-Öl-Phase erfolgt und keine Emulsionen auftreten.Theoretical is a neutralization and thus rendering harmless the acidic decomposition products of chlorinated paraffins are relatively simple To achieve the addition of oil-soluble soaps. This measure is not generally applicable, especially then not if at the same time there is a requirement that the lubricating oil must not emulsify. In such In cases it is essential that the water-oil phase separates quickly and that there is no emulsions appear.
Es wurde nun gefunden, daß das Korrosionsverhalten voniMiueraischmierölen, die Chlorkohlenwasserstoffe wie Chlorparaffine enthalten, verbessert wird, wenn solchen Schmierölen weiterhin als Schanierölzusätze an sich bekannte Glykolmonoalkyläther zugesetzt werden. Glykoknonoalkyläther werden bekanntlich aus Alkoholen und Alkylenoxyd, vorzugsweise Äthylenoxyd, gewonnen. Glykoläther lassen sich durch die allgemeine FormelIt has now been found that the corrosion behavior of iMiueraischmierölen, the chlorinated hydrocarbons such as chlorinated paraffins, is improved if such lubricating oils are continued as hinge oil additives Glycol monoalkyl ethers known per se are added. Glycoconyoalkyl ethers are known obtained from alcohols and alkylene oxide, preferably ethylene oxide. Glycol ethers can be obtained through the general formula
R(OCH2-CHj)0OH (I)R (OCH 2 -CHj) 0 OH (I)
ausdrücken, in der R eine aldphatische Gruppe mit 1 bis 25 C-Atomen ist und η 1 bis 30 ist. Als Beispiel Mineralschmieröleexpress in which R is an aldphatic group with 1 to 25 carbon atoms and η is 1 to 30. As an example, mineral lubricating oils
Anmelder:Applicant:
Esso Research and Engineering Company, Elizabeth, N.J. (V.St.A.)Esso Research and Engineering Company, Elizabeth, N.J. (V.St.A.)
Vertreter: E. Maemecke, Berlin-Lichterfelde West,Representative: E. Maemecke, Berlin-Lichterfelde West,
und Dr. W. Kühl, Hamburg 36, Esplanade 36 a,and Dr. W. Kühl, Hamburg 36, Esplanade 36 a,
PatentanwältePatent attorneys
Alexander von Hoyningen-Huene, Hamburg, ist als Erfinder genannt wordenAlexander von Hoyningen-Huene, Hamburg, has been named as the inventor
ist Äthylenglykolmonoäthyläther zu nennen, welcher die FormelEthylene glycol monoethyl ether is to be called, which has the formula
C2H5O-CH2-CH2OHC 2 H 5 O-CH 2 -CH 2 OH
zukommt.comes to.
Ein einfacher Versuch zaigt, daß die Abspaltung saurer Produkte aus Chlorpamffin bei höheren Ter peraturen bei Anwesenheit einer verhältnismäßig ge ringen Menge eines Glykolmonoalkyläthers gänzlic unterbunden wird: Die Abspaltung sauirer Produkti aus Chlorparaffinen bei höherer Temperatur ist T Verwendung befeuchteter Streifen eines Indifcatoij papiers, welches durch saure Produkte intensiv rötet wird, micht mehr wahrnehmbar.A simple attempt proves that the secession acidic products from Chlorpamffin at higher temperatures in the presence of a relatively ge ring amount of a glycol monoalkyl ether is completely prevented: the splitting off of acidic products from chlorinated paraffins at a higher temperature, T is use of moistened strips of an indifcatoij paper, which is intensely reddened by acidic products, is no longer noticeable.
Zweckmäßig werden Verbindungen der allgemeine Formel (I) in Mengen von 0,01 bis 5 Gewichtsprozen| bezogen auf das Schmieröl, zugesetzt.Compounds of the general formula (I) are expedient in amounts of 0.01 to 5 percent by weight based on the lubricating oil.
Eine weitere Verbesserung im Hinblick auf d| Stabilisierung von Chlorparaffinen kann durch Zusa| einer als Schmiermittelbestandteil ebenfalls an sk bekannten Komponente der allgemeinen FormelAnother improvement in terms of d | Stabilization of chlorinated paraffins can be achieved by adding a component of the general formula which is also known from sk as a lubricant component
HO—(CH2-O—CH2)„—OHHO- (CH 2 -O-CH 2 ) "- OH
erzielt werden, in der η die obige Bedeutung1 hat. Polyglykole sind in Mineralölen verhältnismäßig wenig löslich; ihre Verwendung erfolgt daher unter gleichzeitigem Einsatz von Glykolmonoalkyläthern.can be achieved in which η has the above meaning 1 . Polyglycols are relatively sparingly soluble in mineral oils; they are therefore used with the simultaneous use of glycol monoalkyl ethers.
Vorzugsweise enthält das Schmieröl Verbindungen der allgemeinen Formel (II) in Mengen von 0,01 bis 1 Gewichtsprozent, bezogen auf das Schmieröl.The lubricating oil preferably contains compounds of the general formula (II) in amounts from 0.01 to 1 percent by weight based on the lubricating oil.
Wenn die als Schmiermittelzusatz benutzten handelsüblichen Chlorparaffine einen Stabilisator enthalten, der nach obigen Angaben nicht ausreicht, wenn die Ghlorparaffine auf höherer Temperatur, z. B. 100° C, erhitzt werden, ist darauf zu achten, daß derIf the commercially available chlorinated paraffins used as a lubricant additive contain a stabilizer, which according to the above is not sufficient if the chlorinated paraffins at a higher temperature, eg. B. 100 ° C, care must be taken that the
Stabilisator mit dem erfindungsgemäßen Zusatz au Glykolmonoalkyläther und gegebenenfalls Polyglykol verträglich ist.Stabilizer with the addition of glycol monoalkyl ether according to the invention and optionally polyglycol is compatible.
]](.'ϊ - ρ i el e ]] (. 'ϊ - ρ i el e
1. 5% Chlorparaffin mit 40% Chlor (nach Angabe der Lieferfirma: Höchster Farbwerke) ,1. 5% chlorinated paraffin with 40% chlorine (according to the supplier's information: Höchst Farbwerke) ,
1 % Diglykolmonoäthyläther,
94 % Mineralöl 50 cSt/50° C.1% diglycol monoethyl ether,
94% mineral oil 50 cSt / 50 ° C.
2. 5 % Chlorparaffin mit 50% Chlor (nach Angabe der Lieferfirma: Höchster Farbwerke) ,2. 5% chlorinated paraffin with 50% chlorine (according to the supplier's information: Höchst Farbwerke) ,
'0,8 % Diglykolmonabuty lather.
0,2% Triäthylenglykol.'
94,0% Mineralöl 5O'cSt/5O°C.0.8% diglycol monabuty lather.
0.2% triethylene glycol. '
94.0% mineral oil 50'cSt / 50 ° C.
Chlorparaffinhaltige Mineralölmischungen mit den
erfindiungsgemäßen Zusätzen zeigen gegenüber Fe-Metallen,
auch in Gegenwart von Wasser, keine Korrosionen, die durch saure Abspaltungsprodukte
der Chlorparaffine verursacht werden. Die Zusätze sind somit als Stabilisatoren für Chlorierungsprodukte, besonders Chlorparaffine, anzusprechen.
Vergleichsversuche, über die im folgenden berichtet wird, zeigen die technische Wirkung von chlorparaffinhaltigen
Mineralölmischungen mit den erfindungsgemäßen Zusätzen und ohne die erfindungsgemäßen
Zusätze.Mineral oil mixtures containing chlorinated paraffin with the additives according to the invention show no corrosion to Fe metals, even in the presence of water, which are caused by acidic elimination products of the chlorinated paraffins. The additives are therefore to be addressed as stabilizers for chlorination products, especially chlorinated paraffins.
Comparative tests, which are reported below, show the technical effect of mineral oil mixtures containing chlorinated paraffin with the additives according to the invention and without the additives according to the invention.
ίο Zwei nach verschiedenen Verfahren hergestellte Chlorparaffine (Lieferfirma: Farbwerke Höchst) wurden in Mineralöl gelöst; in diese Lösung wurden Gewichtsteile Wasser eingerührt. In die Mineralölvermischung wurde kohlen stoff armes Tiefziehblech eingeführt und einer Temperatur von 100 bis HO0C ausgesetzt.ίο Two chlorinated paraffins produced by different processes (supplier: Farbwerke Höchst) were dissolved in mineral oil; Parts by weight of water were stirred into this solution. In the oil-lean mixture carbons thermoforming sheet was introduced and subjected to a temperature of 100 to HO 0 C.
Der gleiche Versuch wurde unter Verwendung von Gewichtsprozent einer Mischung A von Diglykolmonobutyläther und Triäthylenglykol (VerhältnisThe same experiment was carried out using percent by weight of a mixture A of diglycol monobutyl ether and triethylene glycol (ratio
so 90:10) durchgeführt.so 90:10).
Mischungmixture
Befund des TiefziehblechesFindings of the deep-drawn sheet
a) 10 Gewichtsprozent Chlorparaffin 1 (40% Cl) 90 Gewichtsprozent Mineralöl 30 cSt/50° Ca) 10 percent by weight chlorinated paraffin 1 (40% Cl) 90 percent by weight mineral oil 30 cSt / 50 ° C
b) 10 Gewichtsprozent Chlorparaffin 2 (40% Cl) 90 Gewichtsprozent Mineralöl 30 cSt/50° Cb) 10 weight percent chlorinated paraffin 2 (40% Cl) 90 weight percent mineral oil 30 cSt / 50 ° C
c) wie a), jedoch mit 1 Gewichtsprozent A c) as a), but with 1 percent A by weight
d) wie b), jedoch mit 1 Gewichtsprozent A d) as b), but with 1 weight percent A
starker Rost nach 4 Stundenstrong rust after 4 hours
starker Rost nach 4 Stundenstrong rust after 4 hours
leichter Rost nach 4 Stunden
leichter Rost nach 4 Stundenlight rust after 4 hours
light rust after 4 hours
Ein Mineralöl wurde auf einen Chlorgehalt von »50% chloriert und mit Lauge gewaschen. Trotzdem
las Produkt zunächst säure- und chlorfrei war, erolgte nach 24 Stunden Lagerung und leichter Erwärnung
erneut intensive Säurespaltung.
« Wurde jedoch etwa 1% eines geeigneten Glykolithers,
z.B. Diglykolmonobutyläther, oder l°/o der dben angeführten Mischung A zugegeben, so konnte
im« Säureabspaltung nicht mehr beobachtet werden. y Die erfindungsmäßigen Zusätze wirken nicht emulrierend
und beeinträchtigen nicht die Hochdruck-Eigenschaften des Schmieröls. Im Bedarfsfall können
~~;ur Erhöhung des Korrosionsschutzes gegen Wasser- -inwiricung übliche, nicht emulgierende Rostschutzmittel
Anwendung finden.A mineral oil was chlorinated to a chlorine content of »50% and washed with lye. In spite of this, the product was initially free of acid and chlorine, but intensive acid cleavage again took place after 24 hours of storage and slight warming.
If, however, about 1% of a suitable glycolite, for example diglycol monobutyl ether, or 1% of the above-mentioned mixture A was added, acid elimination could no longer be observed. y The additives according to the invention do not have an emulsifying effect and do not impair the high-pressure properties of the lubricating oil. If necessary, normal, non-emulsifying anti-rust agents can be used to increase the corrosion protection against exposure to water.
Claims (5)
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE889060X | 1958-11-06 |
Publications (1)
Publication Number | Publication Date |
---|---|
DE1071870B true DE1071870B (en) | 1959-12-24 |
Family
ID=6834385
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
DENDAT1071870D Pending DE1071870B (en) | 1958-11-06 | Mineral lubricating oils |
Country Status (3)
Country | Link |
---|---|
DE (1) | DE1071870B (en) |
FR (1) | FR1238662A (en) |
GB (1) | GB889060A (en) |
-
0
- DE DENDAT1071870D patent/DE1071870B/en active Pending
-
1959
- 1959-09-18 GB GB31855/59A patent/GB889060A/en not_active Expired
- 1959-10-15 FR FR807609A patent/FR1238662A/en not_active Expired
Also Published As
Publication number | Publication date |
---|---|
GB889060A (en) | 1962-02-07 |
FR1238662A (en) | 1960-08-12 |
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