EP0293427B1 - Process for producing a ptfe-dispersion suitable as lubricating oil or as additive for lubricating oils - Google Patents

Process for producing a ptfe-dispersion suitable as lubricating oil or as additive for lubricating oils Download PDF

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EP0293427B1
EP0293427B1 EP87907956A EP87907956A EP0293427B1 EP 0293427 B1 EP0293427 B1 EP 0293427B1 EP 87907956 A EP87907956 A EP 87907956A EP 87907956 A EP87907956 A EP 87907956A EP 0293427 B1 EP0293427 B1 EP 0293427B1
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Prior art keywords
temperature
ptfe
fact
set forth
zone
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German (de)
French (fr)
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EP0293427A1 (en
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Malte Huth
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HUTH, MARC
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HUTH Marc
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    • 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
    • C10M147/00—Lubricating compositions characterised by the additive being a macromolecular compound containing halogen
    • C10M147/02—Monomer 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
    • C10M145/00—Lubricating compositions characterised by the additive being a macromolecular compound containing oxygen
    • C10M145/18—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M145/24—Polyethers
    • C10M145/26—Polyoxyalkylenes
    • C10M145/28—Polyoxyalkylenes of alkylene oxides containing 2 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
    • C10M145/00—Lubricating compositions characterised by the additive being a macromolecular compound containing oxygen
    • C10M145/18—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M145/24—Polyethers
    • C10M145/26—Polyoxyalkylenes
    • C10M145/36—Polyoxyalkylenes 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
    • C10M157/00—Lubricating compositions characterised by the additive being a mixture of two or more macromolecular compounds covered by more than one of the main groups C10M143/00 - C10M155/00, each of these compounds being essential
    • C10M157/02—Lubricating compositions characterised by the additive being a mixture of two or more macromolecular compounds covered by more than one of the main groups C10M143/00 - C10M155/00, each of these compounds being essential at least one of them being a halogen-containing compound
    • 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
    • C10M177/00—Special methods of preparation of lubricating compositions; Chemical modification by after-treatment of components or of the whole of a lubricating composition, not covered by other classes
    • 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
    • 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
    • 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
    • C10M2213/00—Organic macromolecular compounds containing halogen as ingredients in lubricant compositions
    • C10M2213/02—Organic macromolecular compounds containing halogen as ingredients in lubricant compositions obtained from monomers 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
    • C10M2213/00—Organic macromolecular compounds containing halogen as ingredients in lubricant compositions
    • C10M2213/06—Perfluoro polymers
    • C10M2213/062—Polytetrafluoroethylene [PTFE]
    • 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
    • C10N2040/02—Bearings
    • 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
    • C10N2040/25—Internal-combustion engines
    • 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
    • C10N2040/25—Internal-combustion engines
    • C10N2040/251—Alcohol fueled engines
    • 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
    • C10N2040/25—Internal-combustion engines
    • C10N2040/255—Gasoline engines
    • 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
    • C10N2040/25—Internal-combustion engines
    • C10N2040/255—Gasoline engines
    • C10N2040/28—Rotary engines
    • 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
    • C10N2050/015—Dispersions of solid lubricants
    • C10N2050/02—Dispersions of solid lubricants dissolved or suspended in a carrier which subsequently evaporates to leave a lubricant coating
    • 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
    • C10N2070/00—Specific manufacturing methods for lubricant compositions
    • C10N2070/02—Concentrating of additives

Definitions

  • the invention relates to a method for producing a PTFE dispersion in oil as a lubricating oil or lubricating oil additive, PTFE in powder form or as an aqueous dispersion in the presence of a nonionic surfactant as an antistatic agent being mixed with a commercially available mineral oil.
  • Dispersions based on polytetrafluoroethylene (PTFE) which are commercially available under the collective term of oil additives are known to have an extremely low coefficient of friction, so that it makes sense to use them as lubricants, e.g. in engine oil or gear oil or to reduce wear on machine guides, in threads or similar applications in which two friction partners are exposed to high loads.
  • PTFE polytetrafluoroethylene
  • Dispersions based on polytetrafluoroethylene (PTFE) which are commercially available under the collective term of oil additives are known to have an extremely low coefficient of friction, so that it makes sense to use them as lubricants, e.g. in engine oil or gear oil or to reduce wear on machine guides, in threads or similar applications in which two friction partners are exposed to high loads.
  • PTFE is naturally anti-adhesive.
  • Ionogenic PTFE dispersions generally have the disadvantage that they can only be installed in media with a corresponding charge, which means a corresponding application limitation. But even if this prerequisite is met, PTFE agglomeration can be expected after a short period of operation in polluting media such as lubricating oils.
  • the present invention has for its object to provide a method of the generic type, which enables the production of a PTFE dispersion in oil, the desired film formation on metallic surfaces can be realized permanently in its lubricating use and wherein it depends on a certain ionization Oil doesn't arrive.
  • This object is achieved in the generic method in that a permanent attachment of the nonionic surfactant to the PTFE particles is achieved by a subsequent heat treatment with several temperature zones, the mixture first a shock zone with maximum temperature and then one or more tempering zones with increasingly lower Flows through temperatures and the maximum temperature corresponds at most to the limit value for the heat resistance of the surfactant.
  • the PTFE particles it is possible to coat the PTFE particles permanently with a net-active substance in the form of a surfactant, so that their static charge is prevented, or at least considerably reduced, which in turn favors their even wetting of the metal surfaces or enables them in the first place.
  • the PTFE particles thus converted into a neutral charge state adhere to the cathodic metal surface, where they form a thin, homogeneous film, which is responsible for a decisive improvement in the friction behavior of the coated metal surface.
  • the described advantageous effects of the lubricating oil or lubricating oil additive produced by the process according to the invention can be traced back to the heat treatment proposed according to the invention, by means of which the surfactant ions are permanently attached to the PTFE particles.
  • the shock zone causes the charge carriers present on the PTFE to be released; this results in wetting of the PTFE, the charge-free particles of which are permanently coated by the addition of the nonionic surfactant.
  • the subsequent tempering zones prevent the surfactant from decomposing with the surprising one Effect of long-term stable neutrality of the mixture on PTFE with the non-ionic surfactant.
  • the heat treatment according to the invention also ensures that the PTFE aglomerates present in the still untreated mixture dissolve. This creates the essential prerequisites for the formation of a homogeneous PTFE film over the metal surfaces to be treated.
  • the dispersion according to the invention is charge-neutral, it can be used equally well with cationic, anionic and nonionic engine oils. Due to the surfactant coating, the PTFE is no longer accessible to external charge carriers; it can neither agglomerate nor settle. Any sediment that may arise can be redispersed by gentle shaking or stirring.
  • nonylphenol polyglycol ether is used as the surfactant.
  • the maximum temperature used in the shock zone is 280 ° C.
  • two to four tempering zones follow the shock zone, the temperature of the last tempering zone being 40-60 ° C.
  • Three tempering zones are expediently provided, the temperatures in the first and second tempering zones being approximately 200 ° C. and 120 ° C.
  • a particularly advantageous embodiment of the method according to the invention is that the mixture flows at ambient temperature into a flow channel in which the temperature zones corresponding to the heat treatment follow one another, and that the flow channel is extended by a calming section exposed to the ambient temperature, which consists of a PTFE tube .
  • a duct piece lined with PTFE can also be used.
  • the maintenance of the electroneutral properties of the mixture is ensured by the PTFE tube, which advantageously represents the outflow for the finished mixture.
  • the PTFE tube is advantageously extended into the flow channel up to a maximum of the first tempering zone.
  • the PTFE tube expediently extends into the middle tempering zone.
  • a particularly simple procedure provides that the temperature zones follow one another closely along a vertical flow channel. This results in relatively low requirements for the design of the apparatus.
  • a flow channel with mutually insulated, separately temperature-controllable sections is sufficient, for example in the configuration present in known extruders.
  • both the flow rate and the dwell times in the upstream flow sections can be influenced in a simple manner.
  • a flow channel 1 which is composed of four sections 2, 3, 4 and 5 from top to bottom.
  • the temperatures of the individual sections can be regulated independently of one another. Between the sections there is in each case an insert 8 made of a heat-insulating material.
  • a PTFE tube 7 is inserted into the flow channel 1 from below, which forms a so-called calming section and opens directly into a filling container (not shown).
  • Devices for heating the individual sections and for regulating the temperature have been omitted in the drawing for the sake of a clear representation.
  • the uppermost section 2 of the flow channel 1 is connected directly to a filling funnel 6, into which the mixture of the PTFE oil dispersion and the surfactant is filled at an ambient temperature TU of approximately 20 ° C.
  • the process can be carried out in batches or in continuous operation. In the context of the invention, a recirculating operation with multiple recirculation of a batch can also be expedient.
  • the individual sections of the flow channel 1 can have approximately the same length, the total length of the flow channel should be approximately one meter or more.
  • the diameter of the flow channel or the PTFE tube should be selected so that the liquid in the individual sections almost assumes the temperature of the respective section. In a specific exemplary embodiment, the diameter D of the flow channel is approximately twice the PTFE tube, the latter approximately 10 mm, with a liquid throughput of 2-5 liters per minute.
  • the uppermost section 2 corresponds to the shock zone ZO with a temperature TO of approximately 280 ° C.
  • the next section 3 forms a first tempering zone Z1 with a temperature T1 of approximately 200 ° C.
  • the following section 4 forms a middle tempering zone Z2 with a temperature T2 of approximately 120 ° C; the bottom section 5 forms the last tempering zone Z3 with a temperature T3 of about 40-60 ° C.
  • the PTFE tube 7 is inserted from below into the flow channel 1, so that it lies sealingly against the inner wall of the last section 5 and in part of the penultimate section 4.
  • the PTFE tube 7 is calibrated in accordance with a certain quantity of liquid.
  • the essential function of the PTFE tube is to avoid contact of the treated liquid with the steel sections of the flow channel 1 in the area of the low temperatures, ie the PTFE particles in the liquid should not be given an opportunity by wetting metal surfaces before Filling into suitable plastic containers with a charge exchange of the metal surface.
  • the PTFE powder admixed as a disperse phase should be as fine as possible; the preferred particle size of the PTFE agglomerates is between 0.1 and 1.0 micrometers. Investigations under the scanning electron microscope have shown a particle size in the range from 0.2 to 0.3 micrometers.
  • the proportions in the dispersion can either be selected so that a finished lubricating oil or only a lubricating oil additive is formed, the latter being an additive concentrate which is diluted with oil before use.
  • a suitable lubricating oil additive is produced by the process according to the invention in such a way that a mineral oil content of 10% by weight is initially introduced; 0.5% by weight of nonylphenol polyglycol ether and then 2% by weight of PTFE are stirred in until a homogeneous paste is formed. The paste is then mixed with a further 87.5% by weight of mineral oil. This liquid mixture is then subjected to the heat treatment process according to the invention.

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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 process for producing a dispersion of PTFE in oil useful as lubricating oil or as additive for lubricating oils. A wetting mixture is obtained by mixing into the dispersion a non-ionic surfactant as antistatic agent, permanently deposited on the PTFE particles through subsequent heat treatment with several temperature zones.

Description

Die Erfindung betrifft ein Verfahren zur Herstellung einer PTFE-Dispersion in Öl als Schmieröl oder Schmierölzusatz, wobei PTFE in Pulverform oder als wässrige Dispersion in Gegenwart eines nichtionischen Tensids als Antistatikum mit einem handelsüblichen Mineralöl vermischt wird.The invention relates to a method for producing a PTFE dispersion in oil as a lubricating oil or lubricating oil additive, PTFE in powder form or as an aqueous dispersion in the presence of a nonionic surfactant as an antistatic agent being mixed with a commercially available mineral oil.

Ein derartiges Verfahren ist in der deutschen Offenlegungsschrift 27 32 686 beschrieben. Die Bildung einer stabilen Dispersion ist dabei allenfalls zeitlich begrenzt durch Zugabe eines Neutralisationsmittels, z.B. Aluminiumoxid, möglich. Da sich aber die lonenträger insbesondere mit zunehmendeer Verschmutzung des Schmieröls rasch umorientieren, ist kurzfristig mit einem irreversiblen Absetzen agglomerierter PTFE-Teilchen zu rechnen.Such a method is described in German Offenlegungsschrift 27 32 686. The formation of a stable dispersion is at best limited in time by adding a neutralizing agent, e.g. Alumina, possible. However, since the ion carriers rapidly reorient themselves, particularly with increasing contamination of the lubricating oil, an irreversible settling of agglomerated PTFE particles can be expected in the short term.

Im Handel unter dem Sammelbegriff der Öladditive erhältliche Dispersionen auf der Basis von Polytetrafluoräthylen (PTFE) besitzen bekanntermaßen einen extrem niedrigen Reibungskoeffizienten, so daß es naheliegt, sie als Schmiermittelzusatzt z.B. im Motoröl oder Getriebeöl oder zur Verschleißminderung bei Maschinenführungen, in Gewindegängen oder ähnlichen Anwendungsfällen, bei welchen zwei Reibungspartner hohen Lasten ausgesetzt sind, einzusetzen. Die besondere Problematik dieses Einsatzes besteht jedoch darin, daß PTFE von Natur antiadhäsiv ist. In der Dispersion mit Öl kommt es zu einer elektrostatischen Aufladung der PTFE-Partikelchen und damit zu Abstößungsreaktionen gegenüber den zu schmierenden Metalloberflächen.Dispersions based on polytetrafluoroethylene (PTFE) which are commercially available under the collective term of oil additives are known to have an extremely low coefficient of friction, so that it makes sense to use them as lubricants, e.g. in engine oil or gear oil or to reduce wear on machine guides, in threads or similar applications in which two friction partners are exposed to high loads. However, the particular problem with this use is that PTFE is naturally anti-adhesive. In the dispersion with oil, there is an electrostatic charge on the PTFE particles and thus repulsive reactions to the metal surfaces to be lubricated.

Andererseits ist bekannt, das Benetzungsvermögen der Dispersions durch Zugabe von Benetzungsmitteln, sogenannten Tensiden, zu erhöhen. Vor kationischen Dispergenzien wird jedoch gewarnt, da diese besonders in Ölen leicht zum Koagulieren der Dispersion führen.On the other hand, it is known to increase the wetting ability of the dispersions by adding wetting agents, so-called surfactants. However, caution is advised against cationic dispersants, as these easily lead to coagulation of the dispersion, especially in oils.

lonogene PTFE-Dispersionnen haben allgemein den Nachteil, daß sie nur in Medien mit korrespondierender Ladung eingebaut werden können, was eine entsprechende Anwendungsbeschränkung bedeutet. Aber selbst wenn diese Voraussetzung gegeben ist, muß in verschmutzenden Medien wie Schmierölen schon nach kurzer Betriebszeit mit einer PTFE-Agglomeration gerechnet werden.Ionogenic PTFE dispersions generally have the disadvantage that they can only be installed in media with a corresponding charge, which means a corresponding application limitation. But even if this prerequisite is met, PTFE agglomeration can be expected after a short period of operation in polluting media such as lubricating oils.

Demnach läßt sich aufgrund der bekannten Überlegungen die gewünschte dauerhafte Verteilung bzw. Anlagerung der PTFE-Partikel auf einer zu schmierenden Metalloberfläche nicht erzielen.Accordingly, based on the known considerations, the desired permanent distribution or attachment of the PTFE particles on a metal surface to be lubricated cannot be achieved.

Demgegenüber liegt der vorliegenden Erfindung die Aufgabe zugrunde, ein Verfahren der gattungsgemäßen Art zu schaffen, welches die Herstellung einer PTFE-Dispersion in Öl ermöglicht, bei deren schmiertechnischem Einsatz die gewünschte Filmbildung auf metallischen Oberflächen dauerhaft verwirklicht werden kann und wobei es auf einen bestimmten lonisierungszustand des Öls nicht ankommt.In contrast, the present invention has for its object to provide a method of the generic type, which enables the production of a PTFE dispersion in oil, the desired film formation on metallic surfaces can be realized permanently in its lubricating use and wherein it depends on a certain ionization Oil doesn't arrive.

Diese Aufgabe wird bei dem gattungsgemäßen Verfahren dadurch gelöst, daß eine bleibende Anlagerung des nichtionischen Tensids an die PTFE-Partikel durch eine nachfolgende Wärmebehandlung mit mehreren Temperaturzonen erzielt wird, wobei die Mischung zuerst eine Schockzone mit maximaler Temperatur und danach eine oder mehrere Temperzonen mit zunehmend niedrigeren Temperaturen durchstömt und wobei die maximale Temperatur höchstens dem Grenzwert für die Wärmebeständigkeit des Tensids entspricht.This object is achieved in the generic method in that a permanent attachment of the nonionic surfactant to the PTFE particles is achieved by a subsequent heat treatment with several temperature zones, the mixture first a shock zone with maximum temperature and then one or more tempering zones with increasingly lower Flows through temperatures and the maximum temperature corresponds at most to the limit value for the heat resistance of the surfactant.

Nach dieser Verfahrensregel gelingt es, mit einem netzaktiven Stoff in Form eines Tensids die PTFE-Partikeln dauerhaft zu ummanteln, so daß deren statische Aufladung verhindert, zumindest beträchtlich reduziert wird, was wiederum deren gleichmäßige Benetzung der Metalloberflächen begünstigt bzw. überhaupt erst ermöglicht. Die auf diese Weise in einen neutralen Ladungszustand übergeführten PTFE-Partikel bleiben auf der kathodischen Metalloberfläche haften, wo sie einen dünnen homogenen Film bilden, welcher ursächlich ist für eine entscheidende Verbesserung des Reibungsverhaltens der beschichteten Metalloberfläche.According to this process rule, it is possible to coat the PTFE particles permanently with a net-active substance in the form of a surfactant, so that their static charge is prevented, or at least considerably reduced, which in turn favors their even wetting of the metal surfaces or enables them in the first place. The PTFE particles thus converted into a neutral charge state adhere to the cathodic metal surface, where they form a thin, homogeneous film, which is responsible for a decisive improvement in the friction behavior of the coated metal surface.

Diese überraschend vorteilhafte Wirkung konnte durch Versuche eindrucksvoll bestätigt werden. Mit einem nach dem erfindungsgemäßen Verfahren hergestellten Schmierölzusatz beschichtete Metallproben wurden unter dem Elektronenmikroskop untersucht. Bei Bestrahlung mit Elektronen ergab die Elektronenreflexion unscharfe Konturen der Metalloberfläche, verursacht durch den PTFE-Film auf der Metalloberfläche. Nach einer anderen Untersuchungsmethode wurde der Elektronenstrahl des Rasterelektronenmikroskops benutzt, welcher die sich auf der Metalloberfläche befindlichen Elemente zur Aussendung einer charakteristischen Röntgenstrahlung anregt. Die erhaltenen Diagramme zeigten einen Auschnitt des gesamten Spektrums im Wellenlängebiet des Elementes Fluor, welches das charakteristische Element im PTFE darstellt.This surprisingly advantageous effect has been impressively confirmed by tests. Metal samples coated with a lubricating oil additive produced by the method according to the invention were examined under the electron microscope. When irradiated with electrons, the electron reflection resulted in blurred contours of the metal surface, caused by the PTFE film on the metal surface. According to another investigation method, the electron beam of the scanning electron microscope was used, which excites the elements on the metal surface to emit characteristic X-rays. The diagrams obtained showed a section of the entire spectrum in the wavelength region of the element fluorine, which is the characteristic element in PTFE.

Verschleißversuche mittels der Radioisotopenmethode haben überdies die verschleißmindernde Wirkung des erfindungsgemäßen Schmierölzusatzes bestätigt. An einer untersuchten Kolbenringlauffläche ergab sich zwei Stunden nach Zugabe des erfindungsgemäßen Schmierölzusates eine Verschleißminderung von 54%.Wear tests using the radioisotope method have also confirmed the wear-reducing effect of the lubricating oil additive according to the invention. On an examined piston ring running surface, there was a wear reduction of 54% two hours after the addition of the lubricating oil additive according to the invention.

Die beschriebenen vorteilhaften Wirkungen des nach dem erfindungsgemäßen Verfahren hergestellten Schmieröls bzw. Schmierölzusatzes gehen ursächlich zurück auf die erfindungsgemäß vorgeschlagene Wärmebehandlung, durch welche eine bleibende Anlagerung der Tensid-lonen an die PTFE-Partikel erzielt wird. Dabei bewirkt die Schockzone, daß am PTFE vorhandene Ladungsträger abgeben werden; dadurch kommt es zu einer Benetzung des PTFE, dessen ladungsfreie Teilchen durch Anlagerung des nichtionogenen Tensids dauerhaft ummantelt werden. Durch die nachfolgenden Temperzonen wird ein Zersetzen des Tensids verhindert mit der überraschenden Wirkung einer langzeitstabilen Neutralität des Gemisches auf PTFE mit dem nichtionischen Tensid.The described advantageous effects of the lubricating oil or lubricating oil additive produced by the process according to the invention can be traced back to the heat treatment proposed according to the invention, by means of which the surfactant ions are permanently attached to the PTFE particles. The shock zone causes the charge carriers present on the PTFE to be released; this results in wetting of the PTFE, the charge-free particles of which are permanently coated by the addition of the nonionic surfactant. The subsequent tempering zones prevent the surfactant from decomposing with the surprising one Effect of long-term stable neutrality of the mixture on PTFE with the non-ionic surfactant.

Durch die erfindungsgemäße Wärmebehandlung wird ferner erreicht, daß sich die in der noch unbehandelten Mischung vorhandenen PTFE-Aglomerate auflösen. Somit sind die wesentlichen Voraussetzungen für die Bildung eines homogenen PTFE-Films über den zu behandelnden Metalloberflächen geschaffen.The heat treatment according to the invention also ensures that the PTFE aglomerates present in the still untreated mixture dissolve. This creates the essential prerequisites for the formation of a homogeneous PTFE film over the metal surfaces to be treated.

Dadurch, daß die erfindungsgemäße Dispersion ladungsneutral ist kann sie gleichermaßen bei kationischund anionisch sowie nichtionogen aufgebauten Motorölen verwendet werden. Durch die Tensidummantelung ist das PTFE für fremde Ladungsträger nicht mehr zugänglich; es kann sich dadurch weder agglomerieren noch absetzen. Ein gegebenenfalls entstehender Bodensatz läßt sich durch leichtes Schütteln oder Umrühren redispergieren.Because the dispersion according to the invention is charge-neutral, it can be used equally well with cationic, anionic and nonionic engine oils. Due to the surfactant coating, the PTFE is no longer accessible to external charge carriers; it can neither agglomerate nor settle. Any sediment that may arise can be redispersed by gentle shaking or stirring.

In Ausgestaltung der erfingungsgemäßen Verfahrens wird als Tensid Nonylphenolpolyglykolether verwendet. In Anpassung an dieses Tensid beträgt die in der Schockzone angewandte maximale Temperatur 280°C.In one embodiment of the process according to the invention, nonylphenol polyglycol ether is used as the surfactant. In adaptation to this surfactant, the maximum temperature used in the shock zone is 280 ° C.

Nach einem weiteren Vorschlag der Erfindung folgen auf die Schockzone zwei bis vier Temperzonen, wobei die Temperatur der letzten Temperzone 40-60°C beträgt. Zweckmäßig sind drei Temperzonen vorgesehen, wobei die Temperaturen in der ersten und zweiten Temperzone etwa 200°C und 120°C betragen.According to a further proposal of the invention, two to four tempering zones follow the shock zone, the temperature of the last tempering zone being 40-60 ° C. Three tempering zones are expediently provided, the temperatures in the first and second tempering zones being approximately 200 ° C. and 120 ° C.

Eine besonders vorteilhafte Ausgestaltung des erfindungsgemäßen Verfahrens besteht darin, daß die Mischung mit Umgebungstemperatur in einen Strömungskanal strömt, in welchem die der Wärmebehandlung entsprechenden Temperaturzonen aufeinanderfolgen, und daß der Strömungskanal durch eine der Umgebungs temperatur ausgesetzte Beruhigungsstrecke verlängert ist, welche aus einem PTFE-Rohr besteht. Anstelle des PTFE-Rohrs kommt auch ein mit PTFE ausgekleidetes Kanalstück in Frage.A particularly advantageous embodiment of the method according to the invention is that the mixture flows at ambient temperature into a flow channel in which the temperature zones corresponding to the heat treatment follow one another, and that the flow channel is extended by a calming section exposed to the ambient temperature, which consists of a PTFE tube . Instead of the PTFE tube, a duct piece lined with PTFE can also be used.

Durch das PTFE-Rohr, welches vorteilhaft den Abfluß für die fertig behandelte Mischung darstellt wird die Aufrechterhaltung der elektroneutralen Eigenschaften der Mischung gewährleistet.The maintenance of the electroneutral properties of the mixture is ensured by the PTFE tube, which advantageously represents the outflow for the finished mixture.

Das PTFE-Rohr ist vorteilhaft in den Strömungskanal hinein bis maximal zur ersten Temperzone verlängert. Bei Anwendung von drei Temperzonen reicht das PTFE-Rohr zweckmäßig bis in die mittlere Temperzone hinein.The PTFE tube is advantageously extended into the flow channel up to a maximum of the first tempering zone. When using three tempering zones, the PTFE tube expediently extends into the middle tempering zone.

Eine besonders einfache Verfahrensführung sieht vor, daß die Temperaturzonen entlang einem vertikalen Strömungskanal dicht aufeinanderfolgen. Für die apparative Ausgestaltung ergeben sich dabei verhältnismäßig geringe Anforderungen. Es genügt ein Strömungskanal mit voneinander isolierten, getrennt temperaturregelbaren Abschnitten, beispielsweise in der bei bekannten Extrudern vorhandenen Ausgestaltung.A particularly simple procedure provides that the temperature zones follow one another closely along a vertical flow channel. This results in relatively low requirements for the design of the apparatus. A flow channel with mutually insulated, separately temperature-controllable sections is sufficient, for example in the configuration present in known extruders.

Durch geeignete Kalibrierung des PTFE-Rohr können auf einfache Weise sowohl die Durchflußmenge als auch die Verweilzeiten in dem PTFE-Rohr vorgeschalteten Strömungsabschnitten beeinflußt werden.By suitable calibration of the PTFE tube, both the flow rate and the dwell times in the upstream flow sections can be influenced in a simple manner.

Im folgenden wird ein Verfahrensbeispiel anhand der Zeichnung erläutert.A process example is explained below with reference to the drawing.

Diese zeigt in verkürzter Darstellung einen Strömungskanal 1, welcher von oben nach unten aus vier Abschnitten 2, 3, 4 und 5 zusammengesetzt ist. Die Temperaturen der einzelnen Abschnitte sind unabhängig voneinander regelbar Zwischen den Abschnitten befindet sich jeweils eine Einlage 8 aus einem wärmeisolierenden Werkstoff. Von unten her ist in den Strömungskanal 1 ein PTFE-Rohr 7 eingeschoben, welches eine sogenannte Beruhigungsstrecke bildet und unmittelbar in einen nicht dargestellten Abfüllbehälter mündet. Einrichtungen zum Heizen der einzelnen Abschnitte und zum Regeln der Temperatur sind in der Zeichnung zugunsten einer übersichtlichen Darstellung weggelassen.This shows in a shortened representation a flow channel 1, which is composed of four sections 2, 3, 4 and 5 from top to bottom. The temperatures of the individual sections can be regulated independently of one another. Between the sections there is in each case an insert 8 made of a heat-insulating material. A PTFE tube 7 is inserted into the flow channel 1 from below, which forms a so-called calming section and opens directly into a filling container (not shown). Devices for heating the individual sections and for regulating the temperature have been omitted in the drawing for the sake of a clear representation.

Der oberste Abschnitt 2 des Strömungskanals 1 ist unmittelbar an einen Einfülltrichter 6 angeschlossen, in welchen die Mischung aus der PTFE-ÖI-Dispersion und dem Tensid bei einer Umgebungstemperatur TU von etwa 20°C eingefüllt wird. Das Verfahren kann chargenweise oder im Durchlaufbetrieb gefahren werden. Im Rahmen der Erfindung kann auch ein Umlaufbetrieb bei mehrfachem Umlauf einer Charge zweckmäßig sein. Die einzelnen Abschnitte des Strömungskanals 1 können etwa die gleiche Länge aufweisen, wobei die Gesamtlänge des Strömungskanals etwa einen Meter oder darüber betragen sollte. Die Durchmesser des Strömungskanals bzw. des PTFE-Rohrs sind so zu wählen, daß die Flüssigkeit in den einzelnen Abschnitten jeweils nahezu die Temperatur des jeweiligen Abschnitts annimmt. In einem konkreten Ausführungsbeispiel beträgt der Durchmesser D des Strömungskanals etwa das Doppelte des PTFE-Rohrs, letzterer etwa 10 mm, bei einem Flüssigkeitsdurchsatz von 2-5 Liter pro Minute.The uppermost section 2 of the flow channel 1 is connected directly to a filling funnel 6, into which the mixture of the PTFE oil dispersion and the surfactant is filled at an ambient temperature TU of approximately 20 ° C. The process can be carried out in batches or in continuous operation. In the context of the invention, a recirculating operation with multiple recirculation of a batch can also be expedient. The individual sections of the flow channel 1 can have approximately the same length, the total length of the flow channel should be approximately one meter or more. The diameter of the flow channel or the PTFE tube should be selected so that the liquid in the individual sections almost assumes the temperature of the respective section. In a specific exemplary embodiment, the diameter D of the flow channel is approximately twice the PTFE tube, the latter approximately 10 mm, with a liquid throughput of 2-5 liters per minute.

Der oberste Abschnitt 2 entspricht der Schockzone ZO mit einer Temperatur TO von ca. 280°C. Der nächste Abschnitt 3 bildet eine erste Temperzone Z1 mit einer Temperatur T1 von etwa 200°C. Der nachfolgende Abschnitt 4 bildet eine mittlere Temperzone Z2 mit einer Temperatur T2 von ca. 120°C; der unterste Abschnitt 5 bildet die letzte Temperzone Z3 mit einer Temperatur T3 von etwa 40-60°C.The uppermost section 2 corresponds to the shock zone ZO with a temperature TO of approximately 280 ° C. The next section 3 forms a first tempering zone Z1 with a temperature T1 of approximately 200 ° C. The following section 4 forms a middle tempering zone Z2 with a temperature T2 of approximately 120 ° C; the bottom section 5 forms the last tempering zone Z3 with a temperature T3 of about 40-60 ° C.

Das PTFE-Rohr 7 ist von unten in den Strömungskanal 1 eingeschoben, so daß es dichtend an der Innenwand des letzten Abschnittes 5 und zum Teil des vorletzten Abschnittes 4 anliegt. Das PTFE-Rohr 7 ist kalibriert in Abstimmung auf einen bestimmten Mengendurchsatz der Flüssigkeit. Die wesentliche Funktion des PTFE-Rohres besteht darin, eine Berührung der behandelten Flüssigkeit mit den stählernen Abschnitten des Strömungskanals 1 im Bereich der niedrigen Temperaturen zu vermeiden, d.h. den PTFE-Partikeln in der Flüssigkeit soll keine Gelegenheit gegeben werden durch Benetzen von Metalloberflächen bereits vor dem Abfüllen in geeignete Kunststoffbehälter einen Ladungsaustausch mit der Metalloberfläche zu vollziehen.The PTFE tube 7 is inserted from below into the flow channel 1, so that it lies sealingly against the inner wall of the last section 5 and in part of the penultimate section 4. The PTFE tube 7 is calibrated in accordance with a certain quantity of liquid. The essential function of the PTFE tube is to avoid contact of the treated liquid with the steel sections of the flow channel 1 in the area of the low temperatures, ie the PTFE particles in the liquid should not be given an opportunity by wetting metal surfaces before Filling into suitable plastic containers with a charge exchange of the metal surface.

Das als disperse Phase zugemischte PTFE-Pulver soll möglichst fein sein; die bevorzugte Teilchengröße der PTFE-Agglomerate beträgt zwischen 0,1 und 1,0 Mikrometer. Untersuchungen unter dem Rasterelektronenmikroscop haben eine Teilchengröße im Bereich von 0,2 bis 0,3 Mikometer ergeben.The PTFE powder admixed as a disperse phase should be as fine as possible; the preferred particle size of the PTFE agglomerates is between 0.1 and 1.0 micrometers. Investigations under the scanning electron microscope have shown a particle size in the range from 0.2 to 0.3 micrometers.

Als Trägermedium eignet sich jedes einfache Mineralöl, übliche Motor- oder Getriebeöl, bevorzugt paraffinbasische Mineralöle ohne Zusätze. Nach dem erfindungsgemäßen Verfahren können die Verhältnisanteile in der Dispersion entweder so gewählt werden, daß ein fertiges Schmieröle oder nur ein Schmierölzusatz entsteht, wobei letzterer ein Additivkonzentrat darstellt, welches vor der Anwendung noch mit Öl verdünnt wird.Any simple mineral oil, common motor or gear oil, preferably paraffin-based mineral oils without additives, is suitable as a carrier medium. In the process according to the invention, the proportions in the dispersion can either be selected so that a finished lubricating oil or only a lubricating oil additive is formed, the latter being an additive concentrate which is diluted with oil before use.

Beispielsweise erfolgt die Herstellung eines geeigneten Schmierölzusatzes nach dem erfindungsgemäßen Verfahren derart, daß zunächst ein Mineralölanteil von 10 Gew.-% vorgelegt wird; darin werden 0,5 Gew.-% Nonylphenolpolyglykolether und danach 2 Gew.-% PTFE eingerührt bis eine homogene Paste entsteht. Die Paste wird dann mit weiteren 87,5 Gew.-% Mineralöl verrührt. Diese Flüssigkeitsmischung wird dann den erfindungsgemäßen Wärmebehandlungsverfahren unterzogen.For example, a suitable lubricating oil additive is produced by the process according to the invention in such a way that a mineral oil content of 10% by weight is initially introduced; 0.5% by weight of nonylphenol polyglycol ether and then 2% by weight of PTFE are stirred in until a homogeneous paste is formed. The paste is then mixed with a further 87.5% by weight of mineral oil. This liquid mixture is then subjected to the heat treatment process according to the invention.

Für die Anwendung als Zusatz zum Motorenöl empfiehlt sich dessen Mischung mit dem erfindungsgemäß hergestellten Schmierölzusatz im Verhältnis von 4:1 Teilen.For use as an additive to motor oil, it is advisable to mix it with the lubricating oil additive prepared according to the invention in a ratio of 4: 1 parts.

Claims (8)

1. Method for producing a PTFE dispersion in oil as a lubricant or as a lubricating additive whereby PTFE in the form of powder or as an aqueous dispersion is mixed with a commercial mineral oil in the presence of a non-ionic wetting agent serving as an antistatic agent. The method is characterized by a permanent addition of the non-ionic wetting agent to the PTFE particles by means of a subsequent heat treatment in several temperature zones; the mixture initially flows through a shock zone (ZO) at maximum temperature and then is subjected to one or more temperature zones (Z1, Z2, Z3) at progressively lower temperatures, the maximum temperature equals at most the limiting value of the wetting agent decomposition temperature.
2. A method as set forth in claim 1 characterized by the fact that the non-ionic wetting agent is nonylphenol glycol ether and the maximum temperature is 280°C.
3. A method as set forth in claims 1 or 2 characterized by the fact that the shock zone (ZO) is followed by two to four temperature zones whereby the temperature of the last temperature zone is 40°-60°C.
4. A method as set forth in claims 1 to 3 characterized by the fact that there are three temperature zones (Z1, Z2, Z3) whereby temperatures of the first (Z1) and second (Z2) temperature zone are approximately 200° and 120°C respectively.
5. A method as set forth in claim 1 characterized by the fact that the mixture passes through a flow conduit (1), initially at ambient temperature, subsequently through successive heat treatments in successive temperature zones, and by the fact that the flow conduit (1) is extended into a temperature abatement zone having ambient temperature and consisting of a PTFE tube (7).
6. A method as set forth in claim 5 characterized by the fact that the PTFE tube (7) extends into the flow conduit (1), but not further than into the first temperature zone (Z1).
7. A method as set forth in claim 6 characterized by the fact that with three temperature zones (Z1, Z2, Z3) the PTFE tube (7) extends into the central temperature zone (Z2).
8. A method as set forth in claim 5 characterized by the fact that the temperature zones directly follow each other inside a vertical flow conduit (1).
EP87907956A 1986-12-13 1987-12-02 Process for producing a ptfe-dispersion suitable as lubricating oil or as additive for lubricating oils Expired - Lifetime EP0293427B1 (en)

Applications Claiming Priority (2)

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DE3642617 1986-12-13
DE3642617A DE3642617C1 (en) 1986-12-13 1986-12-13 Process for the production of a PTFE dispersion as a lubricating oil or lubricating oil additive

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EP0293427A1 EP0293427A1 (en) 1988-12-07
EP0293427B1 true EP0293427B1 (en) 1990-05-02

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JP (1) JP2527800B2 (en)
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CA2112352A1 (en) * 1991-07-05 1993-01-21 Guy Dion Biro Lubricating composition, preparation process and applications, particularly as an oil additive
US5516556A (en) * 1994-09-23 1996-05-14 Baker; Larry J. Composition for and method of treating skate blades and the like
US6036945A (en) 1997-04-11 2000-03-14 Shamrock Technologies, Inc. Delivery systems for active ingredients including sunscreen actives and methods of making same
US5846447A (en) * 1997-08-26 1998-12-08 E. I. Du Pont De Nemours And Company Process for forming a dispersion of polytetrafluoroethylene
US5990054A (en) * 1997-12-31 1999-11-23 Willis; John Dale Method of mixing diethylene glycol and polytetrafluoroethylene
DE102007055927A1 (en) 2007-12-23 2009-06-25 Leibniz-Institut Für Polymerforschung Dresden E.V. Long-term stable oil-PTFE dispersion and process for its preparation
ITRM20090654A1 (en) * 2009-12-11 2011-06-12 Eon Srl LUBRICATING OILS FOR DIESEL ENGINES WORKING WITH VEGETABLE OILS
DE102011083076A1 (en) 2011-09-20 2013-03-21 Leibniz-Institut Für Polymerforschung Dresden E.V. Process for the preparation of stable oil PTFE dispersions
CN105754689A (en) * 2016-03-16 2016-07-13 巩俭 Protective coating liquid for brake system

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US3432511A (en) * 1961-11-07 1969-03-11 Duriron Co Processing of plastic materials
US4127491A (en) * 1976-07-23 1978-11-28 Michael Ebert Hybrid lubricant including halocarbon oil
US4224173A (en) * 1978-06-12 1980-09-23 Michael Ebert Lubricant oil containing polytetrafluoroethylene and fluorochemical surfactant
US4615817A (en) * 1985-05-17 1986-10-07 Mccoy Frederic C Additives containing polytetrafluoroethylene for making stable lubricants

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EP0293427A1 (en) 1988-12-07
JPH01501634A (en) 1989-06-08
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DE3642617C1 (en) 1988-04-21

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