CH654020A5 - Lubricant for cold-forming of metals - Google Patents

Lubricant for cold-forming of metals Download PDF

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Publication number
CH654020A5
CH654020A5 CH4399/82A CH439982A CH654020A5 CH 654020 A5 CH654020 A5 CH 654020A5 CH 4399/82 A CH4399/82 A CH 4399/82A CH 439982 A CH439982 A CH 439982A CH 654020 A5 CH654020 A5 CH 654020A5
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CH
Switzerland
Prior art keywords
distillation
hydrolysis product
lubricant
residue
vegetable oils
Prior art date
Application number
CH4399/82A
Other languages
German (de)
Inventor
Yakov Moiseevich Zolotovitsky
Venedikt Mikhailovich Zubov
Alexandr Ivanovich Soshko
Vladimir Evgenievi Shestopalov
Valery Isaakovich Markovich
Natalia Nikolaevna Mikhnevich
Nikolai Ivanovich Strikel
Vitaly Julievich Gotgelf
Oleg Vladimirovich Rechkalov
Original Assignee
Sp K Byuro Analit Priborostr
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Application filed by Sp K Byuro Analit Priborostr filed Critical Sp K Byuro Analit Priborostr
Priority to CH4399/82A priority Critical patent/CH654020A5/en
Publication of CH654020A5 publication Critical patent/CH654020A5/en

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    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M169/00Lubricating compositions characterised by containing as components a mixture of at least two types of ingredient selected from base-materials, thickeners or additives, covered by the preceding groups, each of these compounds being essential
    • C10M169/02Mixtures of base-materials and thickeners
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    • C10M101/00Lubricating compositions characterised by the base-material being a mineral or fatty oil
    • C10M101/04Fatty oil fractions
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    • C10M107/00Lubricating compositions characterised by the base-material being a macromolecular compound
    • C10M107/02Hydrocarbon polymers; Hydrocarbon polymers modified by oxidation
    • C10M107/04Polyethene
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    • C10M107/00Lubricating compositions characterised by the base-material being a macromolecular compound
    • C10M107/20Lubricating compositions characterised by the base-material being a macromolecular compound containing oxygen
    • C10M107/22Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M107/24Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to an alcohol, aldehyde, ketonic, ether, ketal or acetal radical
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    • C10M111/00Lubrication compositions characterised by the base-material being a mixture of two or more compounds covered by more than one of the main groups C10M101/00 - C10M109/00, each of these compounds being essential
    • C10M111/04Lubrication compositions characterised by the base-material being a mixture of two or more compounds covered by more than one of the main groups C10M101/00 - C10M109/00, each of these compounds being essential at least one of them being a macromolecular organic compound
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    • C10M119/00Lubricating compositions characterised by the thickener being a macromolecular compound
    • C10M119/04Lubricating compositions characterised by the thickener being a macromolecular compound containing oxygen
    • C10M119/06Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M119/08Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to an alcohol, aldehdo, ketonic, ether, ketal or acetal radical
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    • C10M2205/00Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
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    • C10M2205/02Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers
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    • C10M2205/022Ethene
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    • C10M2205/04Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing aromatic monomers, e.g. styrene
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    • C10M2205/00Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
    • C10M2205/06Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing conjugated dienes
    • C10M2205/066Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing conjugated dienes used as thickening agents
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    • C10M2205/08Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing non-conjugated dienes
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    • C10M2205/10Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing cycloaliphatic monomers
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    • C10M2205/12Oxidised hydrocarbons, i.e. oxidised subsequent to macromolecular formation
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    • C10M2205/00Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
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    • C10M2209/00Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
    • C10M2209/02Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M2209/04Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to an alcohol or ester thereof; bound to an aldehyde, ketonic, ether, ketal or acetal radical
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    • C10M2209/046Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to an alcohol or ester thereof; bound to an aldehyde, ketonic, ether, ketal or acetal radical used as thickening agents
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    • C10N2040/00Specified use or application for which the lubricating composition is intended
    • C10N2040/20Metal working
    • C10N2040/24Metal working without essential removal of material, e.g. forming, gorging, drawing, pressing, stamping, rolling or extruding; Punching metal
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    • C10N2040/241Manufacturing joint-less pipes
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Abstract

A lubricant for cold-forming metals contains a dispersant and a polymeric filling compound. The dispersant used is a mixture of distillation residues from hydrolysis products of animal fats and vegetable oils. The polymeric filling compound is a dispersed polymer. The lubricant has the following ratios of the constituents, in % by mass: - disperse polymer 5 - 15 - residue from the distillation of the hydrolysis product of animal fats 43-50 - residue from the distillation of the hydrolysis product of vegetable oils remainder.

Description

       

  
 

**WARNUNG** Anfang DESC Feld konnte Ende CLMS uberlappen **.

 



   PATENTANSPRÜCHE
1. Schmiermittel für das Kaltformen von Metallen, enthaltend ein Dispersionsmittel und eine polymere Füllmasse, dadurch gekennzeichnet, dass es als Dispersionsmittel ein Gemisch aus Rückständen der Destillation des Hydrolyseproduktes von tierischen Fetten und pflanzlichen Ölen und als polymer Füllmasse ein disperses Polymer mit dem folgenden Verhältnis der genannten Bestandteile in Masse-% enthält: - disperses Polymer 5-15 - Rückstand der Destillation des Hydrolyseproduktes von tierischen Fetten 43-50 - Rückstand der Destillation des Hydrolyseproduktes von pflanzlichen Ölen Rest
2.

  Schmiermittel nach Anspruch 1, dadurch gekennzeichnet, dass es folgende gewichtsmässige Zusammensetzung in Masse-% aufweist: - Niederdruckpolyethylen 10-15 - Rückstand der Destillation des Hydrolyseproduktes von tierischen Fetten 45-50 - Rückstand der Destillation des Hydrolyseproduktes von pflanzlichen Ölen Rest
3. Schmiermittel nach Anspruch 1, gekennzeichnet durch folgende gewichtsmässige Zusammensetzung in Masse-%: - Polyvinylbutyral 5-10 - Rückstand der Destillation des   Hydrolyseproduktes    von tierischen Fetten 47-50 - Rückstand der Destillation des Hydrolyseproduktes von pflanzlichen Ölen Rest
Die Erfindung bezieht sich auf ein Schmiermittel für das Kaltformen von Metallen. Das erfindungsgemässe Schmiermittel kann bei der Metallbearbeitung zur Fertigung von Erzeugnissen aus schwerumformbaren Stoffen verwendet werden.



   Bekannte Schmiermittel, welche für den Einsatz bei der
Fertigung von Erzeugnissen durch plastische Verformung geeignet sind, enthalten gewöhnlich Mineralöle, organische Öle, in organischen Lösungsmitteln gelöste Polymere, anorganische Füllstoffe usw.



   Diese Schmiermittel weisen allerdings niedrige Betriebseigenarten auf und haben sich unter schwierigen Bedingungen der Metallbearbeitung als nicht wirksam erwiesen. Aus diesem Grund sollen neue, für die schwierigen Bedingungen der Metallbearbeitung geeignete Schmiermittel entwickelt werden.



   In dem SU-Urheberschein Nr. 308 799 ist ein Schmiermittel für das Kaltformen (Blechbearbeitung) von Metallen beschrieben, welches eine Lösung von Niederdruckpolyethylen (polymere Füllmasse) in Mineralöl (Dispersionsmittel) enthält.



   Das genannte Schmiermittel auf Basis von Mineralöl hat sich aber wegen seiner ungenügenden Haftung an gleitenden Flächen und niedriger mechanischer Festigkeit des gebildeten Schmierfilms für die Arbeitsgänge des Tiefziehens, besonders bei der Fertigung von Erzeugnissen aus rostfreiem Stahl sowie aus Titan als nicht wirksam erwiesen. Dies ist dadurch bedingt, dass das Mineralöl keine Bruchfestigkeit aufweist und dass in den Lösungen von Polyethylen in Mineralöl geringer Konzentration (von 5 bis 6%) keine Vernetzung erfolgt.



   Das Schmiermittel wird von der Berührungsstelle des Werkstückes aus rostfreiem Stahl und des Ziehwerkzeuges verdrängt. Das erwähnte Schmiermittel kann nur nach vorheriger Bearbeitung der Metalloberfläche, beispielsweise durch Phosphatierung oder Verkupferung, verwendet werden.



   Der Erfindung liegt die Aufgabe zugrunde, ein Schmiermittel zur Verfügung zu stellen, dessen qualitative und quantitative Änderung eine Erhöhung seiner Betriebseigenarten bei der Bearbeitung von schwerumformbaren Metallen durch Bildung eines während der Verformung beständigen Schmierfilms ergibt.



   Die gestellte Aufgabe wird durch ein Schmiermittel für das Kaltformen von Metallen gelöst, das aus einem Dispersionsmittel und einer polymeren Füllmasse besteht und dadurch gekennzeichnet ist, dass es als Dispersionsmittel ein Gemisch aus Rückständen der Destillation des Hydrolyseproduktes von tierischen Fetten und pflanzlichen Ölen und als polymere Füllmasse ein disperses Polymer mit dem folgenden Verhältnis der genannten Komponenten in Masse-% enthält:

  : - disperses Polymer 5-15 - Rückstand der Destillation des Hydrolyseproduktes von tierischen Fetten 43-50 - Rückstand der Destillation des Hydrolyseproduktes von pflanzlichen Ölen Rest
Da die physikalisch-chemischen und physikalisch-mechanischen Eigenschaften des Dispersionsmittels und des Dispersionsmittels und des dispergierten Polymers optimal sind, weist das erfindungsgemässe Schmiermittel hohe Adhäsionseigenschaften auf und bildet auf der Metalloberfläche einen gegen Verformung beständigen   Schmierfilm.    Infogle einer Adsorption von Fett- und Hydroxyfettsäuren, nämlich der Rückstände der Destillation des Hydrolyseproduktes von tierischen Fetten und pflanzlichen Ölen, bildet sich auf der zu behandelnden Metalloberfläche ein   Schmierfllm,    durch welchen das Polymer in der zu verformenden Zone gehalten wird.

  Bei dem wärmemechanischen Abbau des Polymers bilden aktive Makroradikale auf der umzuformenden Metalloberfläche eine Schicht eines Pfropfcopolymers, wodurch die Oberfläche davor geschützt wird, am Ziehwerkzeug zu haften.



   Ein bevorzugtes erfindungsgemässes Schmiermittel, das sich für das Ziehen von Kohlenstoffstahl und Konstruktionsstahl eignet, hat die folgende gewichtsmässige Zusammensetzung (in   Masse- o):    -   -   Niederdruckpolyethylen 10-15 - Rückstand der Destillation des Hydrolyseproduktes von tierischen Fetten 45-50 - Rückstand der Destillation des Hydrolyseproduktes von pflanzlichen Ölen Rest
Es ist vorteilhaft, zum Ziehen von Werkstücken aus rostfreiem Stahl und aus Titan das folgende Schmiermittel einzusetzen, welches folgende Komponenten in Masse-% enthält:

  : - Polyvinylbutyral 5-10 - Rückstand der Destillation des Hydrolyseproduktes von tierischen Fetten 47-50 - Rückstand der Destillation des Hydrolyseproduktes von pflanzlichen Ölen Rest
Unter dem dispersen Polymer wird ein Polymer mit einer Dispersion von 0,2 bis 0,3 mm sowie mit hohen Antifriktionsund filmbildenden Eigenschaften, beispielsweise Polyvinylbutyral oder Niederdruckpolyäthylen u.a., verstanden.



   Unter den pflanzlichen Ölen werden insbesonders Sonnenblumenöl, Baumwollsamenöl, Sojaöl, Palmöl sowie Kokosfette u.a. verstanden.



   Die Rückstände der Destillation des Hydrolyseproduktes von tierischen Fetten und pflanzlichen Ölen kann man wie folgt erhalten: Die Öle werden raffiniert, d.h. sie werden mit einer Alkalilösung bei einer Temperatur von 70 bis 95   0C    neutralisiert. Dann werden Rückstände des Raffinierens in Form eines Gemisches aus den Salzen von Fettsäuren, Glycerin, Phosphatiden, Eiweissstoffen und Produkten der alkalischen Hydrolyse bei einer Temperatur von 90 bis 95   0C    mit konzentrierter Schwefelsäure behandelt. Dabei bilden sich  



  freie Fettsäuren, welche anschliessend destilliert werden. Das Destillat der geklärten Fettsäuren wird bei der Herstellung von Seifen und der Destillationsrückstand bei der Herstellung von Schmiermitteln verwendet. Der Destillationsrückstand ist nicht toxisch und stellt ein bei gewöhnlichen Bedingungen nichtbrennbares Produkt dar. Das Gemisch aus Rückständen der Destillation von tierischen Fetten und pflanzlichen Ölen weist im Vergleich zu den einzelnen Rückständen der Destillation von tierischen Fetten und pflanzlichen Ölen eine höhere mechanische Stabilität auf. Das optimale Molekulargewicht, eine ausreichende Dichte und Viskosität sind augenscheinlich durch die guten Dispersionseigenschaften bedingt.



  Die Vernetzung des Schmiermittels ist seinerseits durch ein günstiges, nahes sowie optimales Verhältnis von gesättigten und ungesättigten Säuren bedingt.



   Das Gemisch aus den Rückständen der Destillation des Hydrolyseproduktes von tierischen Fetten und pflanzlichen Ölen im Verhältnis von 1 zu 1 weist die folgende chemische Zusammensetzung und physikalische Eigenschaften auf: - Fett- und Hydroxyfettsäuren in   Masse-%    43-52 - unverseifbare Stoffe in   Masse- '0    9-10 - Stearine und deren Ester, Farbstoffe in Masse-% bis zu 100 - Dichte in g/cm3 (bei 50    C)    0,94-0,96 - Viskosität in cSt mm2/s (bei 50        C) 15-40 - Säurezahl in mg KOH/g 50-55 - Molekulargewicht 305-310 - Flammpunkt in   0C    250-285
Das Gemisch aus den Rückständen der Destillation des Hydrolyseproduktes von tierischen Fetten und pflanzlichen Ölen wird in einen mit einem Rührwerk versehenen Reaktor eingebracht.

  Bei einer Temperatur von 50 bis 60       C wird in diesen Reaktor das disperse Polymer unter ständigem Rühren eingeführt. Die Dispersion des Polymeres beträgt 0,2 bis 0,3 mm.



   Im weiteren wird die Erfindung an Hand von Ausführungsbeispielen näher erläutert.



  Beispiel 1
Das erfindungsgemässe Schmiermittel für das Kaltformen von Metallen enthält folgende Bestandteile in Masse-%: - Niederdruckpolyethylen 10 - Rückstand der Destillation des Hydrolyseproduktes von Knochenfett 45 - Rückstand der Destillation des Hydrolyseproduktes von Sonnenblumenöl 45
Das erwähnte Schmiermittel wurde beim Ziehen von zylindrischen Bechern mit einem Durchmesser von 40 mm aus einem 0,5 dicken Rohstück in einer Kurbelpresse verwendet. Das Rohstückmaterial enthielt   12%    Chrom,   18%    Nickel,    l00o    Titan und Eisen als Rest.



   Die Ziehkraft bei einem Umformgrad von 2 betrug 35 kN.



  Der maximal erreichbare Umformgrad betrug dabei 2,12.



   Verwendete man jedoch für die gleichen Zwecke das in dem SU-Urheberschein 308 799 beschriebene Schmiermittel, welches   10 /oige    Lösung von Polyethylen in Mineralöl darstellt, so betrug bei einem Umformgrad von 2 die Ziehkraft 39 kN. Der maximal erreichbare Umformgrad betrug dabei 2,05.



  Beispiel 2
Das erfindungsgemässe Schmiermittel für das Kaltformen von Metallen enthält folgende Bestandteile in Masse-%: - Polyvinylbutyral 5 - Rückstand der Destillation des Hydrolyseproduktes von Knochenfett 48 - Rückstand der Destillation des Hydrolyseproduktes von Sonnenblumenöl 47
Dieses Schmiermittel wurde beim Ziehen von zylindrischen Bechern mit einem Durchmesser von 40 mm aus einem 0,5 mm dicken Rohstück in einer Kurbelpresse verwendet.



  Das Rohstückmaterial enthielt 12% Chrom, 18% Nickel, 10% Titan und der Rest war Eisen.



   Die Ziehkraft bei einem Umformgrad von 2 betrug 37,0 kN. Der maximal erreichbare Umformgrad betrug dabei 2,18.



   Verwendet man das in dem SU-Urheberschein 308 799 beschriebene Schmiermittel, welches   5%ige    Lösung von Polyethylen in Mineralöl darstellt, für die gleichen Zwecke, so beträgt bei einem Umformgrad von 2 die Ziehkraft 41,5 kN.



  Der maximal erreichbare Umformgrad betrug dabei 2.



  Beispiel 3
Das erfindungsgemässe Schmiermittel für das Kaltformen von Metallen enthält folgende Bestandteile in Masse-%: - Polyvinylbutyral 8 - Rückstand der Destillation des Hydrolyseproduktes von Knochenfett 45 - Rückstand der Destillation des Hydrolyseproduktes von Baumwollsamenöl 47
Das erwähnte Schmiermittel wurde beim Ziehen von zylindrischen Bechern mit einem Durchmesser von 40 mm aus einem 0,5 mm dicken Rohstück in einer Kurbelpresse verwendet. Das Rohstückmaterial enthielt 12% Chrom, 18% Nikkel, 10% Titan und der Rest war Eisen.



   Die Ziehkraft bei einem Umformgrad von 2 betrug 32,5 kN. Der in diesem Fall maximal erreichbare Umformgrad betrug 2,18.



  Beispiel 4
Das erfindungsgemässe Schmiermittel für das Kaltformen von Metallen enthält foglende Bestandteile in Masse-%: - Niederdruckpolyethylen 10 - Rückstand der Destillation des Hydrolyseproduktes von Knochenfett 45 - Rückstand der Destillation des Hydrolyseproduktes von Sonnenblumenöl 45
Das erwähnte Schmiermittel wurde beim Ziehen einer zylindrischen Kappe mit einem Durchmesser von 33 mm aus einem 0.8 mm dicken Rohstück aus einem unlegierten Stahl mit einem Durchmesser von 75 mm auf einer Ziehanlage verwendet.



   Bei einer Ziehkraft von 36 kN und einer Anpresskraft von 5 kN betrug die Ziehtiefe 25,7 mm.



   Beispiel 5
Das erfindungsgemässe Schmiermittel für das Kaltformen von Metallen enthält folgende Bestandteile in Masse-%: - Niederdruckpolyethylen 10 - Rückstand der Destillation des Hydrolyseproduktes von Knochenfett 45 - Rückstand der Destillation des Hydrolyseproduktes von Baumwollsamenöl 45
Dieses Schmiermittel wurde beim Ziehen einer zylindrischen Kappe mit einem Durchmesser von 33 mm aus einem 0,8 mm dicken Rohstück mit einem Durchmesser von 75 mm auf einer Ziehanlage verwendet. Das Rohstückmaterial enthielt 12% Chrom, 18% Nickel, 10% Titan und als Rest Eisen.



   Bei einer Ziehkraft von 61 kN und   Anpresskraft    von 8 kN betrug die Ziehtiefe 25,7 mm.



  Beispiel 6
Das erfindungsgemässe Schmiermittel für das Kaltformen von Metallen enthält folgende Bestandteile in Masse-%: - Polyvinylbutyral 10 - Rückstand der Destillation  des Hydrolyseproduktes von Knochenfett 45 - Rückstand der Destillation des Hydrolyseproduktes von Baumwollsamenöl 45
Dieses Schmiermittel wurde beim Ziehen von zylindrischen Bechern mit einem Durchmesser von 40 mm aus einem 1,0 mm dicken Rohstück in einer hydraulischen Presse verwendet. Das Rohstückmaterial enthielt 1% Aluminium,   0,07%    Kohlenstoff, 0,2% Eisen, 0,1% Silizium, 0,12% Sauerstoff, 0,3% andere Elemente und der Rest war Titan.



   Bei einem Umformgrad von 2 betrug die Ziehkraft 67,0 kN. Der maximal erreichbare Umformgrad betrug dabei 2,25.



  Beispiel 7
Das erfindungsgemässe Schmiermittel für das Kaltformen von Metallen enthält folgende Bestandteile in   Masse-%:    - Niederdruckpolyethylen 12 - Rückstand der Destillation des Hydrolyseproduktes von Knochenfett 48 - Rückstand der Destillation des Hydrolyseproduktes von Sonnenblumenöl 40
Dieses Schmiermittel wurde beim Ziehen von ringförmigen Erzeugnissen aus einem aus Stahl mit niedrigem Kohlenstoffgehalt gefertigten, 1,5 mm dicken Rohstück in einer Kurbelpresse verwendet. Nach der Fertigung von Erzeugnissen in einer Menge von 5000 trat kein Zerschleissen des Ziehwerkzeugs ein.



  Beispiel 8
Das erfindungsgemässe Schmiermittel für das Kaltformen von Metallen enthält folgende Bestandteile in Masse-%: - Niederdruckpolyethylen 10 - Rückstand der Destillation des Hydrolyseproduktes von Knochenfett 50 - Rückstand der Destillation des Hydrolyseproduktes von Sonnenblumenöl 40
Dieses Schmiermittel wurde beim Pressen von Ringförmlingen aus Kohlenstoffstahl von 48 mm Aussendurchmesser, 24 mm Innendurchmesser und von 40 mm Höhe verwendet.



   Die Reibungszahl betrug dabei 0,027.



  Beispiel 9
Das erfindungsgemässe Schmiermittel für das Kaltformen von Metallen enthält folgende Bestandteile in Masse-%: - Niederdruckpolyethylen 10 - Rückstand der Destillation des Hydrolyseproduktes von Knochenfett 50 - Rückstand der Destillation des Hydrolyseproduktes von Sonnenblumenöl 40
Dieses Schmiermittel wurde beim Pressen von ringförmigen Rohstücken von 48 mm Aussendurchmesser, 24 mm Innendurchmesser und 10 mm Höhe aus einem rostfreien, 10% Chrom,   1 8so    Nickel, 10% Titan und Eisen als Rest enthaltendem Stahl verwendet.



   Weiter oben sind nur einige Ausführungsbeispiele für das erfindungsgemässe Schmiermittel angeführt. Es sind jedoch auch andere, für Fachleute des betroffenen Gebietes augenscheinliche Variationen der Ausführung der Erfindung möglich. Deshalb erstreckt sich die Erfindung nicht nur auf die genannten Beispiele, sie kann durch Änderungen und Ergänzungen vervollständigt werden, welche Wesen und Inhalt der Erfindung, die durch die Patentansprüche bestimmt werden, nicht überschreiten. 



  
 

** WARNING ** beginning of DESC field could overlap end of CLMS **.

 



   PATENT CLAIMS
1. Lubricant for the cold forming of metals, containing a dispersant and a polymeric filler, characterized in that it is a mixture of residues from the distillation of the hydrolysis product of animal fats and vegetable oils as a dispersant and a disperse polymer as a polymeric filler with the following ratio of The above-mentioned constituents in mass% contain: - disperse polymer 5-15 - residue from the distillation of the hydrolysis product from animal fats 43-50 - residue from the distillation of the hydrolysis product from vegetable oils
2nd

  Lubricant according to claim 1, characterized in that it has the following composition by weight in mass%: - low-pressure polyethylene 10-15 - residue from the distillation of the hydrolysis product from animal fats 45-50 - residue from the distillation of the hydrolysis product from vegetable oils
3. Lubricant according to claim 1, characterized by the following composition by weight in% by mass: - polyvinyl butyral 5-10 - residue from the distillation of the hydrolysis product from animal fats 47-50 - residue from the distillation of the hydrolysis product from vegetable oils
The invention relates to a lubricant for cold forming metals. The lubricant according to the invention can be used in metalworking for the manufacture of products from materials which are difficult to form.



   Known lubricants which are used for the
Manufacture of products by plastic deformation are usually mineral oils, organic oils, polymers dissolved in organic solvents, inorganic fillers, etc.



   However, these lubricants have low operating characteristics and have not proven to be effective under difficult metalworking conditions. For this reason, new lubricants suitable for the difficult conditions of metalworking are to be developed.



   In the SU copyright certificate No. 308 799 a lubricant for the cold forming (sheet metal working) of metals is described, which contains a solution of low pressure polyethylene (polymeric filling compound) in mineral oil (dispersing agent).



   The above-mentioned lubricant based on mineral oil has not proven to be effective because of its insufficient adhesion to sliding surfaces and the low mechanical strength of the lubricating film formed for the deep-drawing operations, especially in the manufacture of stainless steel and titanium products. This is due to the fact that the mineral oil has no breaking strength and that there is no crosslinking in the solutions of polyethylene in mineral oil of low concentration (from 5 to 6%).



   The lubricant is displaced from the contact point of the stainless steel workpiece and the drawing tool. The lubricant mentioned can only be used after the metal surface has been processed beforehand, for example by phosphating or copper plating.



   The invention has for its object to provide a lubricant, the qualitative and quantitative change results in an increase in its operating characteristics in the processing of difficult-to-form metals by forming a lubricating film resistant to deformation.



   The object is achieved by a lubricant for the cold forming of metals, which consists of a dispersant and a polymeric filler and is characterized in that it is a dispersant, a mixture of residues from the distillation of the hydrolysis product of animal fats and vegetable oils and as a polymeric filler contains a disperse polymer with the following ratio of the components mentioned in mass%:

  : - disperse polymer 5-15 - residue from the distillation of the hydrolysis product from animal fats 43-50 - residue from the distillation of the hydrolysis product from vegetable oils
Since the physico-chemical and physico-mechanical properties of the dispersing agent and the dispersing agent and the dispersed polymer are optimal, the lubricant according to the invention has high adhesive properties and forms a lubricating film resistant to deformation on the metal surface. As a result of the adsorption of fatty and hydroxy fatty acids, namely the residues from the distillation of the hydrolysis product from animal fats and vegetable oils, a lubricating film is formed on the metal surface to be treated, by means of which the polymer is held in the zone to be deformed.

  During the thermomechanical degradation of the polymer, active macroradicals form a layer of a graft copolymer on the metal surface to be formed, which protects the surface from sticking to the drawing tool.



   A preferred lubricant according to the invention, which is suitable for drawing carbon steel and structural steel, has the following composition by weight (in mass%): - low-pressure polyethylene 10-15 - residue from the distillation of the hydrolysis product from animal fats 45-50 - residue from the distillation of the hydrolysis product of vegetable oils rest
It is advantageous to use the following lubricant, which contains the following components in mass%, to pull workpieces made of stainless steel and titanium:

  : - Polyvinylbutyral 5-10 - residue from the distillation of the hydrolysis product from animal fats 47-50 - residue from the distillation of the hydrolysis product from vegetable oils
The disperse polymer is understood to mean a polymer with a dispersion of 0.2 to 0.3 mm and with high anti-friction and film-forming properties, for example polyvinyl butyral or low-pressure polyethylene and others.



   Vegetable oils include, in particular, sunflower oil, cottonseed oil, soybean oil, palm oil and coconut oil, among others. Roger that.



   The residues from the distillation of the hydrolysis product from animal fats and vegetable oils can be obtained as follows: The oils are refined, i.e. they are neutralized with an alkali solution at a temperature of 70 to 95 0C. Then refining residues are treated in the form of a mixture of the salts of fatty acids, glycerol, phosphatides, proteins and products of alkaline hydrolysis at a temperature of 90 to 95 ° C. with concentrated sulfuric acid. Thereby form



  free fatty acids, which are then distilled. The clarified fatty acid distillate is used in the manufacture of soaps and the distillation residue is used in the manufacture of lubricants. The distillation residue is non-toxic and is a non-combustible product under normal conditions. The mixture of residues from the distillation of animal fats and vegetable oils has a higher mechanical stability compared to the individual residues from the distillation of animal fats and vegetable oils. The optimal molecular weight, sufficient density and viscosity are obviously due to the good dispersion properties.



  The cross-linking of the lubricant is in turn due to a favorable, close and optimal ratio of saturated and unsaturated acids.



   The mixture of the residues from the distillation of the hydrolysis product of animal fats and vegetable oils in a ratio of 1 to 1 has the following chemical composition and physical properties: - fatty and hydroxy fatty acids in mass% 43-52 - unsaponifiable substances in mass - ' 0 9-10 - stearins and their esters, dyes in mass% up to 100 - density in g / cm3 (at 50 C) 0.94-0.96 - viscosity in cSt mm2 / s (at 50 C) 15- 40 - acid number in mg KOH / g 50-55 - molecular weight 305-310 - flash point in 0C 250-285
The mixture of the residues from the distillation of the hydrolysis product from animal fats and vegetable oils is introduced into a reactor provided with a stirrer.

  At a temperature of 50 to 60 C, the disperse polymer is introduced into this reactor with constant stirring. The dispersion of the polymer is 0.2 to 0.3 mm.



   The invention is explained in more detail below on the basis of exemplary embodiments.



  example 1
The lubricant according to the invention for the cold forming of metals contains the following constituents in mass%: low-pressure polyethylene 10 - residue from the distillation of the hydrolysis product from bone fat 45 - residue from the distillation of the hydrolysis product from sunflower oil 45
The lubricant mentioned was used in the drawing of cylindrical cups with a diameter of 40 mm from a 0.5 thick blank in a crank press. The raw material contained 12% chromium, 18% nickel, 100% titanium and iron as the rest.



   The drawing force at a degree of deformation of 2 was 35 kN.



  The maximum achievable degree of deformation was 2.12.



   However, if for the same purposes the lubricant described in SU copyright certificate 308 799, which is a 10% solution of polyethylene in mineral oil, the drawing force was 39 kN with a degree of deformation of 2. The maximum achievable degree of deformation was 2.05.



  Example 2
The lubricant according to the invention for the cold forming of metals contains the following constituents in mass%: - polyvinyl butyral 5 - residue from the distillation of the hydrolysis product from bone fat 48 - residue from the distillation of the hydrolysis product from sunflower oil 47
This lubricant was used to pull 40 mm diameter cylindrical cups from a 0.5 mm thick blank in a crank press.



  The stock material contained 12% chromium, 18% nickel, 10% titanium and the rest was iron.



   The drawing force at a degree of deformation of 2 was 37.0 kN. The maximum achievable degree of deformation was 2.18.



   If the lubricant, which is a 5% solution of polyethylene in mineral oil and is described in the SU copyright certificate 308 799, is used for the same purposes, the drawing force is 41.5 kN with a degree of deformation of 2.



  The maximum achievable degree of deformation was 2.



  Example 3
The lubricant according to the invention for the cold forming of metals contains the following constituents in mass%: - polyvinyl butyral 8 - residue from the distillation of the hydrolysis product from bone fat 45 - residue from the distillation of the hydrolysis product from cottonseed oil 47
The lubricant mentioned was used in the drawing of cylindrical cups with a diameter of 40 mm from a 0.5 mm thick blank in a crank press. The stock material contained 12% chromium, 18% nickel, 10% titanium and the rest was iron.



   The drawing force at a degree of deformation of 2 was 32.5 kN. The maximum achievable degree of deformation in this case was 2.18.



  Example 4
The lubricant according to the invention for the cold forming of metals contains the following constituents in mass%: low-pressure polyethylene 10 - residue from the distillation of the hydrolysis product from bone fat 45 - residue from the distillation of the hydrolysis product from sunflower oil 45
The lubricant mentioned was used when pulling a cylindrical cap with a diameter of 33 mm from a 0.8 mm thick blank made of a non-alloy steel with a diameter of 75 mm on a drawing system.



   With a drawing force of 36 kN and a pressing force of 5 kN, the drawing depth was 25.7 mm.



   Example 5
The lubricant according to the invention for the cold forming of metals contains the following constituents in mass%: low-pressure polyethylene 10 - residue from the distillation of the hydrolysis product from bone fat 45 - residue from the distillation of the hydrolysis product from cottonseed oil 45
This lubricant was used when pulling a 33 mm diameter cylindrical cap from a 0.8 mm thick 75 mm diameter blank on a drawing line. The raw material contained 12% chromium, 18% nickel, 10% titanium and the balance iron.



   With a drawing force of 61 kN and pressing force of 8 kN, the drawing depth was 25.7 mm.



  Example 6
The lubricant according to the invention for the cold forming of metals contains the following constituents in mass%: - polyvinyl butyral 10 - residue from the distillation of the hydrolysis product from bone fat 45 - residue from the distillation of the hydrolysis product from cottonseed oil 45
This lubricant was used to pull 40 mm diameter cylindrical cups from a 1.0 mm thick blank in a hydraulic press. The stock material contained 1% aluminum, 0.07% carbon, 0.2% iron, 0.1% silicon, 0.12% oxygen, 0.3% other elements and the rest was titanium.



   With a degree of deformation of 2, the drawing force was 67.0 kN. The maximum achievable degree of deformation was 2.25.



  Example 7
The lubricant according to the invention for the cold forming of metals contains the following constituents in mass%: low-pressure polyethylene 12 - residue from the distillation of the hydrolysis product from bone fat 48 - residue from the distillation of the hydrolysis product from sunflower oil 40
This lubricant was used in the drawing of ring-shaped products from a 1.5 mm thick blank made of low carbon steel in a crank press. After the production of products in a quantity of 5000, the drawing tool was not worn out.



  Example 8
The lubricant according to the invention for the cold forming of metals contains the following constituents in mass%: low-pressure polyethylene 10 - residue from the distillation of the hydrolysis product from bone fat 50 - residue from the distillation of the hydrolysis product from sunflower oil 40
This lubricant was used in the pressing of carbon steel ring-shaped articles with an outside diameter of 48 mm, an inside diameter of 24 mm and a height of 40 mm.



   The coefficient of friction was 0.027.



  Example 9
The lubricant according to the invention for the cold forming of metals contains the following constituents in mass%: low-pressure polyethylene 10 - residue from the distillation of the hydrolysis product from bone fat 50 - residue from the distillation of the hydrolysis product from sunflower oil 40
This lubricant was used in the pressing of ring-shaped raw pieces with an outer diameter of 48 mm, an inner diameter of 24 mm and a height of 10 mm from a stainless steel containing 10% chromium, 1 8so nickel, 10% titanium and iron as the remainder.



   Only a few exemplary embodiments of the lubricant according to the invention are listed above. However, other variations of the practice of the invention that are apparent to those skilled in the art are also possible. Therefore, the invention extends not only to the examples mentioned, it can be completed by changes and additions, which nature and content of the invention, which are determined by the claims, do not exceed.


    

Claims (3)

PATENTANSPRÜCHE 1. Schmiermittel für das Kaltformen von Metallen, enthaltend ein Dispersionsmittel und eine polymere Füllmasse, dadurch gekennzeichnet, dass es als Dispersionsmittel ein Gemisch aus Rückständen der Destillation des Hydrolyseproduktes von tierischen Fetten und pflanzlichen Ölen und als polymer Füllmasse ein disperses Polymer mit dem folgenden Verhältnis der genannten Bestandteile in Masse-% enthält: - disperses Polymer 5-15 - Rückstand der Destillation des Hydrolyseproduktes von tierischen Fetten 43-50 - Rückstand der Destillation des Hydrolyseproduktes von pflanzlichen Ölen Rest  PATENT CLAIMS 1. Lubricant for the cold forming of metals, containing a dispersant and a polymeric filler, characterized in that it is a mixture of residues from the distillation of the hydrolysis product of animal fats and vegetable oils as a dispersant and a disperse polymer as a polymeric filler with the following ratio of The above-mentioned constituents in mass% contain: - disperse polymer 5-15 - residue from the distillation of the hydrolysis product from animal fats 43-50 - residue from the distillation of the hydrolysis product from vegetable oils 2. 2nd Schmiermittel nach Anspruch 1, dadurch gekennzeichnet, dass es folgende gewichtsmässige Zusammensetzung in Masse-% aufweist: - Niederdruckpolyethylen 10-15 - Rückstand der Destillation des Hydrolyseproduktes von tierischen Fetten 45-50 - Rückstand der Destillation des Hydrolyseproduktes von pflanzlichen Ölen Rest Lubricant according to claim 1, characterized in that it has the following composition by weight in mass%: - low-pressure polyethylene 10-15 - residue from the distillation of the hydrolysis product from animal fats 45-50 - residue from the distillation of the hydrolysis product from vegetable oils 3. Schmiermittel nach Anspruch 1, gekennzeichnet durch folgende gewichtsmässige Zusammensetzung in Masse-%: - Polyvinylbutyral 5-10 - Rückstand der Destillation des Hydrolyseproduktes von tierischen Fetten 47-50 - Rückstand der Destillation des Hydrolyseproduktes von pflanzlichen Ölen Rest Die Erfindung bezieht sich auf ein Schmiermittel für das Kaltformen von Metallen. Das erfindungsgemässe Schmiermittel kann bei der Metallbearbeitung zur Fertigung von Erzeugnissen aus schwerumformbaren Stoffen verwendet werden. 3. Lubricant according to claim 1, characterized by the following composition by weight in% by mass: - polyvinyl butyral 5-10 - residue from the distillation of the hydrolysis product from animal fats 47-50 - residue from the distillation of the hydrolysis product from vegetable oils The invention relates to a lubricant for cold forming metals. The lubricant according to the invention can be used in metalworking for the manufacture of products from materials which are difficult to form. Bekannte Schmiermittel, welche für den Einsatz bei der Fertigung von Erzeugnissen durch plastische Verformung geeignet sind, enthalten gewöhnlich Mineralöle, organische Öle, in organischen Lösungsmitteln gelöste Polymere, anorganische Füllstoffe usw.  Known lubricants which are used for the Manufacture of products by plastic deformation are usually mineral oils, organic oils, polymers dissolved in organic solvents, inorganic fillers, etc. Diese Schmiermittel weisen allerdings niedrige Betriebseigenarten auf und haben sich unter schwierigen Bedingungen der Metallbearbeitung als nicht wirksam erwiesen. Aus diesem Grund sollen neue, für die schwierigen Bedingungen der Metallbearbeitung geeignete Schmiermittel entwickelt werden.  However, these lubricants have low operating characteristics and have not proven to be effective under difficult metalworking conditions. For this reason, new lubricants suitable for the difficult conditions of metalworking are to be developed. In dem SU-Urheberschein Nr. 308 799 ist ein Schmiermittel für das Kaltformen (Blechbearbeitung) von Metallen beschrieben, welches eine Lösung von Niederdruckpolyethylen (polymere Füllmasse) in Mineralöl (Dispersionsmittel) enthält.  In the SU copyright certificate No. 308 799 a lubricant for the cold forming (sheet metal working) of metals is described, which contains a solution of low pressure polyethylene (polymeric filling compound) in mineral oil (dispersing agent). Das genannte Schmiermittel auf Basis von Mineralöl hat sich aber wegen seiner ungenügenden Haftung an gleitenden Flächen und niedriger mechanischer Festigkeit des gebildeten Schmierfilms für die Arbeitsgänge des Tiefziehens, besonders bei der Fertigung von Erzeugnissen aus rostfreiem Stahl sowie aus Titan als nicht wirksam erwiesen. Dies ist dadurch bedingt, dass das Mineralöl keine Bruchfestigkeit aufweist und dass in den Lösungen von Polyethylen in Mineralöl geringer Konzentration (von 5 bis 6%) keine Vernetzung erfolgt.  The above-mentioned lubricant based on mineral oil has not proven to be effective because of its insufficient adhesion to sliding surfaces and the low mechanical strength of the lubricating film formed for the deep-drawing operations, especially in the manufacture of stainless steel and titanium products. This is due to the fact that the mineral oil has no breaking strength and that there is no crosslinking in the solutions of polyethylene in mineral oil of low concentration (from 5 to 6%). Das Schmiermittel wird von der Berührungsstelle des Werkstückes aus rostfreiem Stahl und des Ziehwerkzeuges verdrängt. Das erwähnte Schmiermittel kann nur nach vorheriger Bearbeitung der Metalloberfläche, beispielsweise durch Phosphatierung oder Verkupferung, verwendet werden.  The lubricant is displaced from the contact point of the stainless steel workpiece and the drawing tool. The lubricant mentioned can only be used after the metal surface has been processed beforehand, for example by phosphating or copper plating. Der Erfindung liegt die Aufgabe zugrunde, ein Schmiermittel zur Verfügung zu stellen, dessen qualitative und quantitative Änderung eine Erhöhung seiner Betriebseigenarten bei der Bearbeitung von schwerumformbaren Metallen durch Bildung eines während der Verformung beständigen Schmierfilms ergibt.  The invention has for its object to provide a lubricant, the qualitative and quantitative change results in an increase in its operating characteristics in the processing of difficult-to-form metals by forming a lubricating film resistant to deformation. Die gestellte Aufgabe wird durch ein Schmiermittel für das Kaltformen von Metallen gelöst, das aus einem Dispersionsmittel und einer polymeren Füllmasse besteht und dadurch gekennzeichnet ist, dass es als Dispersionsmittel ein Gemisch aus Rückständen der Destillation des Hydrolyseproduktes von tierischen Fetten und pflanzlichen Ölen und als polymere Füllmasse ein disperses Polymer mit dem folgenden Verhältnis der genannten Komponenten in Masse-% enthält:  The object is achieved by a lubricant for the cold forming of metals, which consists of a dispersant and a polymeric filler and is characterized in that it is a dispersant, a mixture of residues from the distillation of the hydrolysis product of animal fats and vegetable oils and as a polymeric filler contains a disperse polymer with the following ratio of the components mentioned in mass%: : - disperses Polymer 5-15 - Rückstand der Destillation des Hydrolyseproduktes von tierischen Fetten 43-50 - Rückstand der Destillation des Hydrolyseproduktes von pflanzlichen Ölen Rest Da die physikalisch-chemischen und physikalisch-mechanischen Eigenschaften des Dispersionsmittels und des Dispersionsmittels und des dispergierten Polymers optimal sind, weist das erfindungsgemässe Schmiermittel hohe Adhäsionseigenschaften auf und bildet auf der Metalloberfläche einen gegen Verformung beständigen Schmierfilm. Infogle einer Adsorption von Fett- und Hydroxyfettsäuren, nämlich der Rückstände der Destillation des Hydrolyseproduktes von tierischen Fetten und pflanzlichen Ölen, bildet sich auf der zu behandelnden Metalloberfläche ein Schmierfllm, durch welchen das Polymer in der zu verformenden Zone gehalten wird. : - disperse polymer 5-15 - residue from the distillation of the hydrolysis product from animal fats 43-50 - residue from the distillation of the hydrolysis product from vegetable oils Since the physico-chemical and physico-mechanical properties of the dispersing agent and the dispersing agent and the dispersed polymer are optimal, the lubricant according to the invention has high adhesive properties and forms a lubricating film resistant to deformation on the metal surface. As a result of the adsorption of fatty and hydroxy fatty acids, namely the residues from the distillation of the hydrolysis product from animal fats and vegetable oils, a lubricating film is formed on the metal surface to be treated, by means of which the polymer is held in the zone to be deformed. Bei dem wärmemechanischen Abbau des Polymers bilden aktive Makroradikale auf der umzuformenden Metalloberfläche eine Schicht eines Pfropfcopolymers, wodurch die Oberfläche davor geschützt wird, am Ziehwerkzeug zu haften. During the thermomechanical degradation of the polymer, active macroradicals form a layer of a graft copolymer on the metal surface to be formed, which protects the surface from sticking to the drawing tool. Ein bevorzugtes erfindungsgemässes Schmiermittel, das sich für das Ziehen von Kohlenstoffstahl und Konstruktionsstahl eignet, hat die folgende gewichtsmässige Zusammensetzung (in Masse- o): - - Niederdruckpolyethylen 10-15 - Rückstand der Destillation des Hydrolyseproduktes von tierischen Fetten 45-50 - Rückstand der Destillation des Hydrolyseproduktes von pflanzlichen Ölen Rest Es ist vorteilhaft, zum Ziehen von Werkstücken aus rostfreiem Stahl und aus Titan das folgende Schmiermittel einzusetzen, welches folgende Komponenten in Masse-% enthält:  A preferred lubricant according to the invention, which is suitable for drawing carbon steel and structural steel, has the following composition by weight (in mass%): - low-pressure polyethylene 10-15 - residue from the distillation of the hydrolysis product from animal fats 45-50 - residue from the distillation of the hydrolysis product of vegetable oils rest It is advantageous to use the following lubricant, which contains the following components in mass%, to pull workpieces made of stainless steel and titanium: : - Polyvinylbutyral 5-10 - Rückstand der Destillation des Hydrolyseproduktes von tierischen Fetten 47-50 - Rückstand der Destillation des Hydrolyseproduktes von pflanzlichen Ölen Rest Unter dem dispersen Polymer wird ein Polymer mit einer Dispersion von 0,2 bis 0,3 mm sowie mit hohen Antifriktionsund filmbildenden Eigenschaften, beispielsweise Polyvinylbutyral oder Niederdruckpolyäthylen u.a., verstanden. : - Polyvinylbutyral 5-10 - residue from the distillation of the hydrolysis product from animal fats 47-50 - residue from the distillation of the hydrolysis product from vegetable oils The disperse polymer is understood to mean a polymer with a dispersion of 0.2 to 0.3 mm and with high anti-friction and film-forming properties, for example polyvinyl butyral or low-pressure polyethylene and others. Unter den pflanzlichen Ölen werden insbesonders Sonnenblumenöl, Baumwollsamenöl, Sojaöl, Palmöl sowie Kokosfette u.a. verstanden.  Vegetable oils include, in particular, sunflower oil, cottonseed oil, soybean oil, palm oil and coconut oil, among others. Roger that. Die Rückstände der Destillation des Hydrolyseproduktes von tierischen Fetten und pflanzlichen Ölen kann man wie folgt erhalten: Die Öle werden raffiniert, d.h. sie werden mit einer Alkalilösung bei einer Temperatur von 70 bis 95 0C neutralisiert. Dann werden Rückstände des Raffinierens in Form eines Gemisches aus den Salzen von Fettsäuren, Glycerin, Phosphatiden, Eiweissstoffen und Produkten der alkalischen Hydrolyse bei einer Temperatur von 90 bis 95 0C mit konzentrierter Schwefelsäure behandelt. Dabei bilden sich **WARNUNG** Ende CLMS Feld konnte Anfang DESC uberlappen**.  The residues from the distillation of the hydrolysis product from animal fats and vegetable oils can be obtained as follows: The oils are refined, i.e. they are neutralized with an alkali solution at a temperature of 70 to 95 0C. Then refining residues are treated in the form of a mixture of the salts of fatty acids, glycerol, phosphatides, proteins and products of alkaline hydrolysis at a temperature of 90 to 95 ° C. with concentrated sulfuric acid. Thereby form ** WARNING ** End of CLMS field could overlap beginning of DESC **.
CH4399/82A 1982-07-19 1982-07-19 Lubricant for cold-forming of metals CH654020A5 (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1944352A1 (en) * 2007-01-12 2008-07-16 Korea Houghton Corporation Biodegradable grease composition using distillation residue generated in production of biodiesel
EP1944353A1 (en) * 2007-01-12 2008-07-16 Korea Houghton Corporation Composition of water-soluble metal working fluid using distillation residue generated in production of biodiesel

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1944352A1 (en) * 2007-01-12 2008-07-16 Korea Houghton Corporation Biodegradable grease composition using distillation residue generated in production of biodiesel
EP1944353A1 (en) * 2007-01-12 2008-07-16 Korea Houghton Corporation Composition of water-soluble metal working fluid using distillation residue generated in production of biodiesel

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