DE3712133C2 - - Google Patents

Abstract

A lubricant or lubricant concentrate derived from mineral and/or synthetic oils possessing improved lubricating properties, in particular improved load-bearing, sliding and anti-corrosion properties, contains a) one or more mineral and/or synthetic oils as the basic oil, b) at least one (OH)4 to (OH)8 alcohol with at least one quaternary carbon atom and at least one ester bond in the molecule, and having a density d20 of at least 0.900 and an enthalpy H of at least 350 kcal/kg, c) at least one asymmetrical organo-metallic compound, d) at least one phosphorus carrier, e) at least one sulphur carrier, and f) other usual additives.

Description

The invention relates to a lubricant or Schmiermit telkonzentrat with improved lubricating properties, ins special improved load carrying, sliding and corrosion protective properties on the basis of mineral and / or Synthetic oil which is a compound having at least one quar tary carbon atom and at least one ester bond in the Molecule and other common additives.

During the last decades numerous procedures have been carried out and lubricant systems designed to work on moving machines Sharing reduces friction and wear, thus reducing energy and he lower part costs and the life of the lubricants and extend materials. An ideal lubricant The "Lifetime Lubricant", which is also the more urgent accommodating ecological demands.

Towards long-term and high-performance lubricants, Lubricating systems and lubrication was in the first Stage the so-called chemical wear lubrication ent wraps. With their help, by applying chemical reactive surface layers on surfaces or by Einbrin supply of chemically reactive compounds in base lubricants the metal-to-metal contact by salt formation at the upper surfaces of the micro mountains of moving parts largely under to be bound. In this way, the seizing of the Machine parts are prevented. At the same time but was the ongoing wear by shearing the salt layers promoted against each other during the movement of the metal parts. The life of the materials therefore remained relatively short. In a further stage were solid lubricants developed, which inserted between the moving metal parts were brought, such. As graphite, MoS₂, TiO₂, Ca₃ (PO₄) ₂, Teflon and the like, which are used as lubricious topcoats, Sus pensions, pastes or fats were introduced. Thereby  the friction partners were better separated from each other and increased their capacity. In centripetal movements higher peripheral speed and at higher temperature However, the solid lubricants and carrier media separate sooner or later from each other due to their differences specific densities. The long-term lubrication were this limits. In a further step succeeded it, from chemical complexes dissolved in a lubricant out suitable metal cations on rubbing surfaces during operation. They form under there Pressure and temperature of the friction partners Eutektikas with the Metal edge layers smoothing the roughness valleys fill up and the roughness splash partly tribochemical, partially flattened microplastically. The anionic part of organometallic compounds forms lubricating and in situ Adhesive reaction layers on the freshly formed eutectoid friction surfaces.

In addition to a too long run-in phase, too high Friction coefficient and abrasion has increased in these Lubricating systems controlling the reaction process as proved problematic.

Either you came to material-independent eutectic and reaction layers producing a fine abrasion conditional material unevenness in tight fits not made more sufficient, so that in these places About Lastungsbereiche emerged, leading to later metal outbreaks led to the sliding surfaces, or it was the aggressive Kom reinforced component of organometallic compounds and With that you got back into the phase of chemical wear lubrication with too high erosion rate and thus too short life.  

From DE-PS 9 41 678, for example, lubricating oils with a content of soluble reaction products of phosphorus pentasulfide with liquid or solid aliphatic carbons hydrogen or terpene hydrocarbons. Out DE-PS 9 23 984 a lubricating oil is known, the metallhal tiger Alkylphenolsulfidester in combination with zinc sulfo contains data. From DE-AS 14 44 892 is a lubricating oil known to be a salt of an aromatic zinc dithio phosphate and a zinc carboxylic acid salt in the presence of Contains water. While the first two products Represent the latter Product to prevent corrosion of silver bearing surfaces. From DE-AS 12 96 730 a lubricating oil is known, the one Salt of a substituted succinic acid, given if together with a salt of an alkylated or ver esterified phosphoric acid. It is an anti detergent oxidant. From DE-AS 12 71 878 is a combination of dithiophosphate and Dithiophosphinatsalzen known. From DE-OS 15 94 555 are cutting oils containing free sulfur, a Dialkyl dithiophosphate and a chlorinated hydrocarbon substance known. From US-PS 34 62 367 are lubricating oils Containing zinc or antimony thiocarbamate be known. From the US-PS 27 58 087 lubricating oils are known, which contain a sulfur-phosphorus compound by Implementation of phosphorus pentasulfide with an olefin at higher temperature is obtained and the zinc phthalate contains. All these known lubricating oil additives satisfy the  no longer meet today's requirements, in particular they lead too strong oxidic deposits in the area of the lubricants cause and cause excessive abrasion. From US-PS 27 34 865 it is known a To use lubricating oil additive, which consists of a dithiophosphate the alkaline earth salts in combination with a complex Um Substitution product of phosphorus sulfides, Tallölfettsäureal koester, zinc chloride and barium hydroxide is formed. The achievable friction coefficients and abrasion values are however, for today's requirements too high, beyond is their surface pressure too low. From the US PS 27 34 864 lubricating oil additives are also known, the a dithiophosphate of alkaline earth salts in combination with a complex reaction product of phosphorus sulfides, Wool fat and alcohol esters are formed. The undefined Product contains significant amounts of barium and zinc. Such a lubricating oil additive is already because of its uner odor, which also comes into contact with it Persons at risk, not in practice usable. From DE-PS 19 54 452 are lubricants the basis of mineral oil or synthetic oil known in addition to the mineral or synthetic oil as additives an ester of a epoxidized fatty acid having 10 to 18 C atoms with or without polyhydric alcohols, an alkyl, aralkyl or aryldi thiophosphate of zinc, lead, tin, tungsten, molybdenum, niobium or lanthanum and optionally a Schwefelphosphorver binding included. DE-PS 21 08 780 are lubricants based on mineral or synthetic oil or lubricant Concentrates known in addition to one with alkyl, aryl or Aralkyl groups esterified lead, tungsten, molybdenum and / or Vanadium dithiophosphate still at least one Zinkdialkyldithio phosphate and a metal-free sulfur-phosphorus compound contain. Also these last mentioned lubricants, the one have found widespread application, meet the requirements modifications to modern long-term and high-performance lubricants no longer in all respects. Your friction Coefficient and abrasion are too high, their storage life is insufficient, in long-term use shows too high Re Clearing rate in the lubrication sector.  

From DE-OS 25 20 459 it is already known, pentaery thritic and / or dipentaerythritol esters of linear sown saturated fatty acids having 7 to 18 carbon atoms Use lubricant or lubricant additive. In GB-PS 21 34 538 are lubricating oil compositions be from 5 to 70% by weight of a mineral oil and / or synthetic oil and the remainder of an ester of a sterically hindered alcohol and an unsaturated one Consist of fatty acid with 18 carbon atoms. Also from the DE-OS 20 34 383 it is already known mixtures of syn thetic esters as additives in lubricants verwen the. The specific mixtures described therein best esterified trimethylolpropane esters of aliphati rule C₄-C₁₂ monocarboxylic acids and esterified dipentaery thritestern of aliphatic C₄-C₁₀ monocarboxylic acids. al len these known lubricant additives is common, that with regard to their lubricating properties, in particular their anti-wear properties, today's ge Increasing requirements are no longer sufficient.

The object of the invention was therefore to provide a lubricant or Lubricant concentrate based on mineral and / or To create synthetic oil, which in terms of its Lubricating properties, especially its friction and Ver Wear protection properties, the state of the art over meets and thus feels the need for energy and spare parts bar and thus also the highest level requirements.

It has now been found that this object according to the invention can be solved by a mineral and / or Synthetic oil in addition to the usual additives at least 4- to 8wertiger alcohol with at least one quaternary Koh and at least one ester bond in the mole and with a critical density and a critical one Enthalpy, an additional component with at least ei ner free hydroxyl group in the molecule, at least one spe  zifische Metalldialkyldithiocarbamatverbindung of standing specified general formula, at least one specific organophosphite and a thiazole added the.

The invention is a Lubricant or lubricant concentrate on the basis of mineral and / or synthetic oil which is a compound with min at least one quaternary carbon atom and at least one Contains ester bond in the molecule and other conventional additives, characterized in that it contains

• (a) at least one 4- to 8-valent alcohol having at least a quaternary carbon atom in the molecule with a density d₂₀ of at least 0.900 and an enthalpy H of at least 350 kcal / kg, selected from the group of mono-, di- and tripentaerythrits whose alko holische hydroxyl group (s) by an acid with unbranched or branched the alkyl, aralkyl or aryl group having 6 to 18 carbon is esterified or ethoxyesterified (are),
• (b) an additional component with at least one free one Hydroxyl group in the molecule,
• (C) at least one Metalldialkyldithiocarbamat of the formula in which mean:
  Me is a metal from the group consisting of copper, silver, zinc, cadmium, boron, titanium, zirconium, tin, lead, vanadium, talc, antimony, chromium, molybdenum, tungsten, manganese, cobalt and nickel and
  Alkyl is an alkyl group having 4 to 8 carbon atoms,
• (d) at least one dialkylaryl, monoalkyldiaryl, trialkyl or triaryl phosphite in which the alkyl group is unbranched, ver is branched or cyclic and has 8 to 12 carbon atoms has
• (e) a thiazole and
• (f) as further customary additives per se known antioxidant tion agents, metal deactivators, detergents, dispersants medium, antifoam and / or viscosity index insurance agent.

Preferably, the lubricant according to the invention contains or lubricant concentrate as another component

• (g) at least one metal dialkyldithiophosphate of the general formula in which mean:
  Me is a metal from the group of copper, silver, zinc, cadmium, boron, titanium, zirconium, tin, lead, vanadium, tantalum, antonone, chromium, molybdenum, tungsten, manganese, cobalt and nickel and
  Alkyl is an alkyl group having 4 to 8 carbon atoms.

The amount in which components (c) and (g) are used is preferably 0.1 to 10 wt .-%, in particular 0.1 to 5 wt .-%, especially 1 to 3 wt .-%.

Further preferred embodiments of the invention Lubricant or lubricant concentrate result from the dependent claims 3 to 9.  

The lubricant or lubricant con centrate wise over the known lubricants or lubricant concentrates significantly improved greasiness in particular with regard to friction and wear, and thus a reduced energy and spare parts may open. It is believed that this is back to it lead is that when used in friction and Gleitbe rich metallic glass surfaces of amorphous solidified metal Melt that no metal crystal lattice structures more have arise. The glassy smooth friction and Sliding surfaces with the lubricant of the invention or lubricant concentrate are presumed to be produced, significantly improve the overall lubrication process, since the Friction coefficient and with it the abrasion, the oxidation and the corrosion can be lowered considerably. Also the so-called Fretting corrosion is caused by the lubricant according to the invention or lubricant concentrate prevented. In addition, that the lubricant or lubricant con Centrates are extremely environmentally friendly as they barely Lead, no sulfurized whale oil and hardly any phosphorus contain. These have fish tests, rat tests and Bacterial growth tests with the inventive Lubricants or lubricant concentrates performed were shown. It was also found that they already within 3 to 4 months in normal soil too at least 60% biodegradable so that they are also extremely environmentally friendly can be designated. They are particularly well suited for use in homokinetic joints for vehicles, d. H. small joints with a high speed and a high Load, and they are considered as an ideal lubricant "Lifetime Lubricant" is much closer than any known lubricant. In addition, the erfindungsge according to used, quaternary carbon atoms containing polyolester Compounds are thermally very stable and therefore high Be allow operating temperatures of up to 300 ° C. They open therefore the possibility for lifetime lubrication hochbe lastet engines, turbines, bearings, constant velocity joints and other high performance machine elements.  

As used herein, the term "lubricant or Lubricant concentrate based on mineral and / or Synthetic oil "are both lubricating oils and greases on a mineral and / or synthetic oil basis to understand.

Among quaternary carbon-containing compounds Here are those compounds in which the four major valences of at least one carbon atom each Molecule occupied by four carbon atoms. Examples for such compounds are mono-, di- and trimer Pentaerythritol ester, pentaerythritolethoxy ester and telomeric acid pentaerythritol ester and the ent speaking ethoxylated ester.

The lubricants or lubricant concentrates according to the invention have trate towards the known lubricants or Lubricant concentrates significantly improved properties on, as the examples below below show. The produced by the lubricant according to the invention glassy glat The friction and sliding surfaces save energy and reduce friction coefficient of coefficient per se and by building a very adherent Grenzschmierfilms, the one Elastohydrodynamische lubrication even with punctiform load allows. This will the friction temperature of lubricant and lubrication point herabge sets, the oxidation resistance of both extended and the metallic friction partner less specific alternating load and temperature-stressed.

Overall, the effects of wear are extraordinary dienst humbled and the life of the friction partners and of the lubricant significantly increased. According to the invention these improvements within a very broad viscous scored so that now also oils with lower Viscosity can be used where previously high or medium viscosity levels as absolutely necessary have been seen, for example in transmissions, differential driven or turbine reduction gears. Also allowed the thermal stability of the lubricant according to the invention by means of or lubricant concentrate its use Lubrication points high operating temperature, for example in diesel engines and aircraft turbines.  

According to the above definition of the invention the lubricant or lubricant concentrate as a compo (a) mono-, di- or tripentaerythritol, the alcoholic Hydroxyl group (s) by an acid with unbranched or branched Alkyl, aralkyl or aryl group of 6 to 18 carbon atoms, preferably 6 to 12 carbon atoms, in particular from 8 to 12 carbon atoms, esterified or ethoxyver estert is (are).

According to the above definition of the invention the lubricant or lubricant concentrate in addition a component (b) with at least one free one Hydroxyl group.

The lubricant or lubricant concentrate according to the invention Step 2 contains component (a) according to another zugten embodiment of the invention in an amount of 0.1 to 40 wt .-%, preferably from 0.1 to 20 wt .-%, in particular especially from 1 to 12% by weight, especially from 2 to 6% by weight, based on the weight of the mineral and / or synthetic oil.

According to a further preferred embodiment of the invention Contains the lubricant or lubricant according to the invention telkonzentrat as component (a) an ester and / or ethoxylated ester derivative of mono-, di- or tripenta erythritol and / or a telomeric acid pentaerythritol ester or an ethoxylated derivative thereof.

As a base oil contains the lubricant according to the invention or Lubricant concentrate preferably rapeseed oil, natural oil and / or a synthetic oil having a viscosity in the range of 1.0 mPa · s at 20 ° C to 2 x 10⁶ mPa · s at 20 ° C. Especially before zugt is the use of a mineral oil with a Visko  of 1.0 mPa · s at 20 ° C to 540 mPa · s at 50 ° C as Natural oil as well as the use of an aromatic or alipha dicarboxylic acid esters, in particular poly-α-olefin dicarboxylic acid ester, especially butyl ester, with one Molecular weight in the range of 1000 to 3000, preferably example of diisodecyl phthalate, trimethyladipic acid didecyl ester and sebacic acid dioctyl ester, a polyiso Butylene with a molecular weight of 1000 to 100,000 and a viscosity of 200 to 43,000 mPa · s at 100 ° C, a polymethacrylate with a Viskosi of 1000 mPa · s at 100 ° C, a non-water soluble Polyglycol having a viscosity of 5 to 60 mPa · s at 100 ° C, an isoparaffin oil and / or alkylbenzene with a flame point above 50 ° C and a viscosity in the range of 1.0 mPa · s at 20 ° C at 2,000,000 mPa · s at 20 ° c and a telo mersäureesters, preferably a Neopentylglykol- or Trimethylolpropane ester of the telomeric acid.

As a further additive, the lubricant according to the invention contains medium or lubricant concentrate Thiazole, at least one Metalldialkyldithiocarbamat and an organophosphite, preferably a dialkylaryl phosphite, especially didecylphenyl phosphite or didodecylphenyl phosphite as well optionally at least one Metalldialkyldithiophosphat.

The thiazole is preferably in an amount of 0.5 to 10 wt .-%, in particular from 1 to 3 wt .-%, in the Contain lubricant or lubricant concentrate, wäh it preferably contains the phosphite in an amount of 0.1 to 5 wt .-% in particular from 0.5 to 2% by weight.

As further customary additives, the inventive Lubricant or lubricant concentrate usual anti oxidants, metal deactivators, detergents, Dispersant, antifoam and / or viscosity index improvers.  

Other features and advantages of the invention will become apparent from the description below.

To the 4- to 8-valent Al used in the invention koholen with at least one quaternary carbon atom in Molecule include the following compounds:

a) Esters and ethoxylated esters of mono-, di- and tripentaerythritol

The underlying mono- and dipentaerythritol has the structure:

in which the hydroxyl group (s) by an acid with straight or branched alkyl, aralkyl or aryl groups of 6 to 18 preferably 8 to 12, carbon atoms is (are) esterified.

These compounds are easy to manufacture and pay rich representatives of these compounds are in commerce festlich, for example, by the company Ciba-Geigy the trade names Reolube LP 3600® (pentaerythritol tetrapelargonat), Reolube, LPE 504® (pentaerythritol tetraoctyl ester), Reolube LPE 602® (pentaerythritol tetraheptyl ester), from Akzo under the trade name Ketjenlube 12® (pentaerythritol tetradecyl / dodecyl ester with statistical  C₁₀ / C₁₂ distribution), and from the company Henkel AG under the Trade name Edenor Ke 230® (pentaerythritol tetraisopalmitic acid ester) and pentaerythritol tetraisostearic acid ester.

Examples of suitable pentaerythritol esters are the tetrahexyl, tetraoctyl, tetranonyl, tetradecyl, Tetradodecyl, tetramyristyl, tetrahexadecyl, tetra stearyl, tetraoleyl, tetraisostearyl and tetraisopalmitin acid ester of pentaerythritol.

b) Pentaerythrittelomeric acid derivatives having the following basic structure

in which mean:
T = telomere
R = T or alkyl

Telomeric acids are known to be verbin with relatively high molecular weights and  long-chain, star-like branched structures on usual way can be esterified and their esters worth represent full lubricants (commercial product Kortacid T the company Akzo Chemie).

Mineral oils which can be used according to the invention are all customary Mineral oils of isoparaffin oil with a viscosity of 1.0 mPa · s at 20 ° C over thin spindle oil with a viscosity of 12 mPa · s at 20 ° C to high viscosity brightstock and cylin oil with a viscosity of 540 mPa · s at 50 ° C.

Many of the synthetic oils useful in this invention are commercially available, for example from the company BP under the trademark "Hyvis 10" (a polyisobutylene with a viscosity at 100 ° C of 200 mPa · s), "Hyvis 200" (a polyisobutylene having a viscosity at 100 ° C of 4300 mPa · s) and "Hyvis 2000" (a polyisobutylene with a viscosity at 100 ° C of 43,000 mPa · s), "Viscoplex 4-95" from Röhm (a polymethacrylate) with egg ner viscosity of 1000 mPa · s at 100 ° C, "Ucolub N9" with egg ner viscosity of 5.7 mPa · s at 100 ° C, "Ucolub N36A" with egg ner viscosity of 18 mPa · s at 100 ° C, "Ucolub N 120A" with egg ner viscosity of 55 mPa · s at 100 ° C (all non-aqueous polyglycols) of Union Carbide, as well as "Isopar J" from the company Esso (an isoparaffin oil) with a Viscosity at 20 ° C of 1.0 mPa · s.

In the invention usable as a phosphorus carrier Organophosphorus compounds are compounds the formula

wherein each R is a straight-chain, branched or cyclic alkyl group having 6 to 12 carbon atoms or aryl group mean.

Preferred examples of organophosphorus compounds of the above mentioned formula are monodecyl-diphenyl phosphite, dide  cylphenyl phosphite, triphenyl phosphite, dioctyl phenyl phosphite, Dihexyl phenyl phosphite, diisodecyl phenyl phosphite, Diisooctyl-phenyl-phosphite, didecyl-o-methylphenyl phosphite and didecyl-p-methylphenyl phosphite.

In the metal used in the invention Dialkyldithiocarbamaten are compounds of formula

where Me is a metal from the group consisting of copper, silver, zinc, Cadmium, boron, titanium, zirconium, tin, lead, vanadium, tan tal, antimony, chromium, molybdenum, tungsten, manganese, and Kolbalt Nickel, preferably boron, nickel, cobalt or molybdenum means.

In the invention usable metal dialkyl dithiophos phaten are compounds of the formula

where Me is a metal from the group copper, silver, Zinc, cadmium, boron, titanium, zirconium, tin, lead, vanadium, Tantalum, antimony, chromium, molybdenum, tungsten, manganese, cobalt and nickel, preferably for zinc, nickel, titanium, vanadium, Molybdenum, tungsten and manganese, stands.

The alkyl group in the above-mentioned Metalldialkyldithio  carbamates and Metalldialkyldithiophosphaten contains each 4 to 8 carbon atoms, so that said Metal salts in the commercial base oils still soluble are. Examples of particularly advantageous alkyl groups include the n-, i- and tert-butyl group, the n- and i-amyl group, the n- and i-hexyl group, the n- and i-heptyl group and the 2-ethylhexyl group. Very particularly preferred are the i-butyl group, the n- and i-amyl groups and the 2- Ethylhexyl.

Examples of inventive ver with particular advantage reversible metal dialkyldithiocarbamates are the following: Kupferdialkyldithiocarbamate and Kupferbisdialkyldithio carbammate; Silberdialkyldithiocarbamate; Zinc and cadmium bisdialkyldithiocarbamate; Bortrisdialkyldithiocarbamate; Titanium, zirconium, tin and lead tetrakisdialkyldithio carbamates, and tin and bis-bis-dialkyl dithiocarbamates; Antimony, vanadium and tantalum trialkyldithiocarbamates, tetrakis and pentakisdialkyldithiocarbamates and the Dialkyldithiocarbamates in which these metals in mixture th oxidation states are present; Chromium Bomb, Chromium Tris, Chromium tetrakis and chromium hexakisdialkyldithiocarbamates, Molybdenum and tungsten tetrakis, hexakis and oxybis and oxy tetrakisdialkyl dithiocarbamates; Manganis, tris and -hexakisdialkyldithiocarbamate; and cobalt and nickel bis- and -tis-dialkyldithiocarbamates.

Among these compounds, particularly preferred are the Bortrisdialkyldithiocarbamate, the Nickeltrisdialkyl dithiocarbamate and the molybdenum tetrakis and molybdenoxy tetrakisdialkyldithiocarbamate.

Metalldialkyldithiophophate according to the invention with can be used to particular advantage are the Dialkyldithiophosphate of the same metals in the same chen oxidation states as above for the Metalldialkyldi  thiocarbamate have been enumerated.

Very particularly advantageous are zinc bisdialkyldithiophos phate, nickel bis- and tris-dialkyl dithiophosphates, titanium and vanadium tetrakisdialkyldithiophosphates, molybdenum and Tungsten tetrakisdialkyldithiophosphate and molybdenum and Wolframoxytetrakisdialkyldithiophosphate.

Particularly preferred representatives of the invention verwen The metal dialkyldithiocarbamates are:

Boron trisdiisobutyl dithiocarbamate, boron triadiyldi thiocarbamate, boron trisdi-2-ethylhexyl dithiocarbamate, nickeltrisdiisobutyldithiocarbamate, Nickel trisdiamyl dithiocarbamate, nickel trisdi-2-ethylhexyl dithiocarbamate, molybdenum tetrakisdi-2-ethylhexyldithio carbamate, molybdenum oxytetrakisdi-2-ethylhexyldithiocarb amate and cobalt bisdiisobutyldithiocarbamate.

Particularly preferred representatives of the invention verwen The metal dialkyldithiophosphates are zinc bisdi-2-ethyl hexyldithiophosphate, nickel bis- and trisdi-2-ethylhexyldi thiophosphate, titanium and vanadium tetrakis-2-ethylhexyl dithiophosphate and molybdenum and tungsten tetrakis and Molybdenoxy and tungsten oxytetrakis-2-ethylhexyldi thiophosphate.

The invention will be explained in more detail by the following examples tert.

In the examples described below, respectively Commercially available lubricating oils or greases with the specified Compositions once with and once without the invention appropriate lubricant concentrate on their lubricating properties investigated and the results achieved compared to each other.

The results obtained are included in the attached Diagrams graphed.  

To carry out the experiments was a circular disc made of stainless steel with a diameter of 23 mm and a Thickness of 10 mm used, on the surface of which a drop of the respective lubricating oil or grease to be examined was applied. In the place where the smear oil or grease, was a ball of the same Stainless steel with a diameter of 10 mm applied, because of their stress a pressure on the surface the metal disc exerted. The metal ball was with a Frequency of 50 Hz over an amplitude of 1 mm for 60-180 min under load on the surface of the metal disc and moved, with the load during the experiment within the range of 50 to 300 N and the tempera were varied within the range of 50 to 150 ° C. (SRV = vibration-friction-wear device of Optimol GmbH).

Because of the friction between the loaded ball and the surface of the metal disk within the experiment Periodically generated wear profile across the oscillation Direction of the ball was by means of a suitable Aufzeich recorded, with the enclosed The diagrams were obtained in which on the ordinate the wear height as the difference between the highest and the lowest point of the surface profile of the metal disk depending on the scanning distance of the surface of Metal disc is shown on the abscissa.

In the accompanying diagrams corresponds to a tread depth on the ordinate of 1 cm of a real tread depth in the Surface of the metal disc of 1 micron with the exception of Diagram B 'of Example 2. This corresponds to a profile depth of 1 cm of a real tread depth of 2.5 microns.  

The diagrams were recorded under otherwise identical conditions (load on the ball 50 to 300 N, friction frequency 50 Hz, temperature 50 to 150 ° C., friction amplitude 1 mm, test duration 1 to 3 h). The friction coefficients given below the diagrams (R _K max = maximum friction coefficient, R _K d = average coefficient of friction over 80% of the friction coefficient curve) were likewise measured with the above-mentioned SRV device. In all experiments, unless otherwise stated, the product of the following composition was used as the lubricant concentrate according to the invention:

50% Pentaerythritol tetraoctyl ester (Ciba 602® from Ciba AG) 20% Copolymer of α-olefinic acid carboxylic acid butanol ester (Ketjenlube 135® from Akzo) 3% Polyalkylene glycol (EMKAROX VG 380® from ICI, Hamburg) 6.5% Trimethyladipinsäuredidecylester 2.5% didecylphenylphosphite 9% Molybdenum di (2-ethylhexyl dithiophosphate) / molybdenum di (2-ethylhexyl di-thiocarbamate) (1: 4) 7% Ethyl hexyl thiadiazole (Amoco 158® from Amoco) 2% Bis-2,6-di-tert-butyl phenol

Example 1

It became a highly viscous lubricating oil with a viscosity of 2200 mPa · s at 50 ° C of the following composition manufactured and tested:

Trimethyladipinsäuredidecylester | 34% Polyisobutylene 43,000 mPa · s / 100 ° C 32% Lubricant drag substance 6% Inventive lubricant concentrate 28%

In the comparative product was the inventive lubricating medium concentrate omitted.

Both products were kept at a temperature of 1 h for 1 h 150 ° C and a load of 200 N under identical loading conditions tested. The results obtained are in the joined diagrams A (according to the invention) and A '(according to Stand the technique) graphically.

With the lubricant additive of the invention resulted a profile depth of 0.80 μm (mean of two measurements). Without the lubricant additive of the invention resulted a tread depth of 1.68 (mean of two measurements).

example 2

It became a medium viscosity lubricating oil with a viscosity from 190 to 200 mPa · s at 50 ° C of the following composition manufactured:

polymeric α-olefin esters (Ketjenlube 135®) | 12% Trimethyladipinsäuredidecylester 36% Polyisobutylene 4300 mPa · s / 100 ° C 18% Lubricant drag substance 6% Inventive lubricant concentrate 28%

The comparative product was the inventive lubricating medium concentrate omitted.

The experiments were carried out under identical conditions for 1 h at a temperature of 150 ° C and a load of 200 N performed. In doing so, the attached dia B and B 'graphically presented results achieved. While using the lubricant of the invention the profile depth at 0.875 μm (average of two mes the tread depth when using the Comparative product 13.98 microns.

example 3

It became a lubricating oil medium viscosity of 120 to 150 mPa.s at 50 ° C with the following composition Composition:

high viscosity α-olefin ester copolymer (Ketjenlube 165) | 4% medium-viscosity α-olefin ester polymer (Ketjenlube 135® 12% Trimethyladipinsäuredidecylester 34% Polyisobutylene 200 mPa · s / 100 ° C 12% Lubricant drag substance 6% Inventive concentrate 32%

In the comparative product was the inventive lubricating medium concentrate omitted.

The experiments were carried out under identical conditions for 1 h at a temperature of 150 ° C and a load of 200 N performed. The results obtained are in the attached diagrams C (according to the invention) and C ' (Comparative product) shown graphically.  

The tread depth when using the lubricating invention oil was 1.12 μm (average of three measurements). The Profile depth when using the comparison product was 3.48 μm.

example 4

It became a highly viscous adhesive and high temperature lubricant Oil with a viscosity of 15 000 mPa · s at 50 ° C with the prepared according to the following composition:

Trimethyladipinsäuredidecylester | 29% Polyisobutylene 43,000 mPa · s / 100 ° C 52% Inventive lubricant concentrate 19%

As a comparative product, the same lubricating oil without the used lubricant concentrate according to the invention.

The experiments were carried out at a temperature of 150 ° C for 1 h and a load of 200 N under identical conditions carried out.

When using the lubricating oil according to the invention was Tread depth 0.80 μm, (average of three measurements), while the tread depth when using the reference product 1.57 microns, as the accompanying diagrams D (erfindungsge and D '(comparative product).

example 5

It was a grease for multi-purpose lubrication highest loaded gearbox and constant velocity joints of the following Composition produced:

Mineral oil SAE 80 (solvent raffinate HR80) | 70% Bodying agent based on lithium stearate 9% Inventive lubricant concentrate 21%

As a comparative product, the same grease was without the lubricant concentrate according to the invention, but with 3 wt .-% molybdenum disulfide / graphite mixture as an additive used. The experiments were carried out at a temperature of 50 ° C for 3 hours and a load of 300 N carried out at otherwise identical conditions.

When using the lubricating grease according to the invention the profile depth 0.95 μm (average of three measurements), while the tread depth when using the reference product 1.63 μm (average of three measurements) was, like the attached diagrams E (according to the invention) and E '(Ver same product).  

Comparative test

Further comparative tests were carried out on the same way as in the previous examples described, but in compliance with the following identical test conditions (if nothing else specified): load 200 N; Temperature 125 ° C; Duration of the test 2 hours.

The compositions used in these experiments Lubricant test samples (a) to (h) according to the invention and (i) according to the prior art, as described by DE-OS 20 34 383 is represented as well as the achieved Results are summarized in the following table.

The sample (a) corresponds to a sample according to the invention, those without the use of a Metalldialkyldithiophosphats and using only Metalldialkyldithiocarbamaten prepared as an additive has been.

The samples (b) to (h) are also inventive Samples, wherein the samples (e), (f) and (g), the one have identical composition, only by it distinguished that they are at different temperatures (100 ° C / 1 h or 130 ° C / 1 h or 150 ° C / 1 h in said Order were tested.

The sample (i) is a sample according to the prior art, represented by DE-OS 20 34 383, as an additive next the pentaerythritol still zinc di- (2-ethylhexyl dithiophosphate contained. This comparative sample was included 200 N / 150 ° C / 1 h tested.

As can be seen from the SRVs summarized in the following table: Wear test results, were the Lubricant samples according to the invention throughout about the  Factor 10 (considering the test duration) better in regarding the wear protection effect (better Lubricating action) as the product according to the prior art, wherein the samples of the invention also in different temperatures were significantly improved (Samples (e) to (h)).  

table

Claims (9)

1. lubricant or lubricant concentrate based on mineral and / or synthetic oil containing a connec tion with at least one quaternary carbon atom and at least one ester bond in the molecule and other üb Liche additives, characterized in that it contains

• a) at least one 4- to 8-valent alcohol having at least one quaternary carbon atom in the molecule with a density d₂₀ of at least 0.900 and an enthalpy H of at least 350 kcal / kg, selected from the group of mono-, di- and Tripentaerythrite whose alcoholic hydroxyl group (n) is esterified or ethoxylated by an acid of unbranched or branched alkyl, aralkyl or aryl group of 6 to 18 carbon atoms
• b) an additional component having at least one free hydroxyl group in the molecule,
• (C) at least one Metalldialkyldithiocarbamat of the formula in which mean:
  Me is a metal from the group consisting of copper, silver, zinc, cadmium, boron, titanium, zirconium, tin, lead, vanadium, talc, antimony, chromium, molybdenum, tungsten, manganese, cobalt and nickel and
  Alkyl is an alkyl group having 4 to 8 carbon atoms,
• d) at least one dialkylaryl, monoalkyldiaryl, trialkyl or triaryl phosphite, in which the alkyl group is unbranched, branched or cyclic and has from 8 to 12 carbon atoms,
• e) a thiazole and
• f) as further customary additives per se known antioxidant tion agents, metal deactivators, detergents, dispersants, antifoams and / or Viskositätsindexverbesse medium.

2. lubricant or lubricant concentrate according to claim 1, characterized in that it holds ent as a further component

• (g) at least one metal dialkyldithiophosphate of the general formula in which mean:
  Me is a metal from the group of copper, silver, zinc, cadmium, boron, titanium, zirconium, tin, lead, vanadium, tantalum, antonone, chromium, molybdenum, tungsten, manganese, cobalt and nickel and
  Alkyl is an alkyl group having 4 to 8 carbon atoms.

3. lubricant or lubricant concentrate according to claim 2, characterized in that it is boron tris diisobutyl dithiocar bamate and / or boron trisdi-2-ethylhexyldithiocarbamate in combi nation with nickel trisdiisobutyl dithiocarbamate, nickel trisdi amyldithiocarbamate and / or nickeltrisdi-2-ethylhexyldithio carbamate and zinc bisdi-2-ethylhexyl dithiophosphate, nickel tris-di-2-ethylhexyl dithiophosphate, titanium tetrakisdi-2-ethyl hexyl dithiophosphate, vanadium tetrakisdi-2-ethylhexyl dithio phosphate, molybdenum tetrakis or molybdenum oxytetrakisdi-2 ethylhexyl dithiophosphate, tungsten tetrakis and / or tungsten oxytetrakisdi-2-ethylhexyl dithiophosphate contains. 4. Lubricant or lubricant concentrate after a of claims 1 to 3, characterized in that it is the Component (a) in an amount of 0.1 to 40 wt .-%, preferably from 0.1 to 20 wt .-%, in particular 1 to 12 wt .-%, spe 2 to 6% by weight, based on the weight of the mineral and / or synthetic oil.   5. lubricant or lubricant concentrate according to one of Claims 1 to 4, characterized in that it as a base oil Rapeseed oil, natural oil and / or a synthetic oil with a viscosity in Range of 1.0 to 2 × 10⁶ mPa · s at 20 ° C. 6. lubricant or lubricant concentrate according to claim 5, characterized in that it is a mineral oil as natural oil with a viscosity of 1.0 mPa · s at 20 ° C to 540 mPa · s at 50 ° C and / or as a synthetic oil an aromatic or alipha dicarboxylic acid esters, in particular poly-α-olefin dicar Bicester, especially butyl ester, with a Molekularge in the range of 1000 to 3000, preferably phthalic acid redisodecyl ester, trimethyl adipic acid dicylate and Se bacic acid dioctyl ester, a polyisobutylene with a molecule largeweight of 1000 to 100 000 and a viscosity of 200 to 43,000 mPa · s at 100 ° C, a polymethacrylate with egg ner viscosity of 1000 mPa · s at 100 ° C, a non-water soluble polyglycol having a viscosity of 5 to 60 mPa · s at 100 ° C, an isoparaffin oil and / or alkylbenzene with a Flash point of over 50 ° C and a viscosity in the range of 1.0 to 2,000,000 mPa · s at 20 ° C and / or a telomeric acid ester, preferably a neopentyl glycol or trimethylol propane ester of the telomeric acid. 7. Lubricant or lubricant concentrate according to one of the An Claims 1 to 6, characterized in that it contains the component (s) (c) and optionally (g) in an amount of 0.1 to 10 wt .-%, preferably from 0.1 to 5 wt .-%, in particular from 0.1 to 3 wt .-%, contains. 8. Lubricant or lubricant concentrate after a of claims 1 to 7, characterized in that it the thiazole in an amount of 0.5 to 10 wt .-%, preferably 1 to 3 wt .-%, contains. 9. Lubricant or lubricant concentrate after a of claims 1 to 8, characterized in that it the phosphite in an amount of 0.1 to 5 wt .-%, preferably 0.5 to 2 wt .-%, contains.