EP2164935A1

EP2164935A1 - Lubricating grease composition

Info

Publication number: EP2164935A1
Application number: EP08758645A
Authority: EP
Inventors: Günther BODESHEIM; Martin Schmidt-Amelunxen; Dieter Sohn; Stefan Grundei; Andrea HÖPKE
Original assignee: Klueber Lubrication Muenchen GmbH and Co KG
Current assignee: Klueber Lubrication Muenchen GmbH and Co KG
Priority date: 2007-06-20
Filing date: 2008-05-20
Publication date: 2010-03-24
Anticipated expiration: 2028-05-20
Also published as: RU2010101286A; ES2563407T3; KR20090130247A; BRPI0811885B1; JP5496087B2; CN101679899A; BRPI0811885A2; KR101216353B1; CA2687149C; JP2010530446A; US20100105586A1; WO2008154997A1; CA2687149A1; DE102008024284A1; RU2480516C2; EP2164935B1; PL2164935T3; KR20120049385A; MX2009013879A; CN101679899B

Abstract

The invention relates to lubricating grease compositions, having a base oil mixture based on oils having viscosities (ISO VG 2 to ISO VG 1500) that are standard for industrial lubricants, an ionic liquid, a thickening agent, e.g. based on a polyurea compound and conventional additives that can be used at current service temperatures that are higher than 120°C to 260°C, in particular at a service temperature in the region of high service temperatures that are higher than 180°C to 260°C and also at low temperatures as low as -6O°C. The invention also relates to a method for producing said type of lubricating grease compositions.

Description

Grease composition

description

The invention relates to lubricating grease compositions which comprise a base oil mixture based on oils having viscosities customary for industrial lubricants (ISO VG 2 to ISO VG 1500), an ionic liquid, a thickener based on a polyurea compound, for example, and customary additives which are suitable both at normal use temperatures of more than 120 ⁰ C to 260 ⁰ C in particular at a service temperature in the range of more than 18O ⁰ C to 260 ⁰ C and at low temperatures to -60 ⁰ C are used. The invention also relates to a process for the preparation of such grease compositions.

The development of new lubricants must be accompanied by the general advancement of technology which places new and higher demands on lubricant compositions. These requirements are no longer equal to the known lubricant compositions based on mineral oil and / or synthetic oil.

Lubricants are used in vehicle technology, materials handling, mechanical engineering, office technology, as well as in industrial plants and machines, but also in the fields of household appliances and consumer electronics. In rolling and plain bearings lubricants ensure that between separating sliding or rolling parts a separating, load-transmitting lubricating film is built up. This ensures that the metallic surfaces do not touch and thus no wear occurs. The lubricants must therefore meet high requirements. These include extreme operating conditions, such as very high or very low speeds, high temperatures due to high speeds or foreign heating, very low temperatures, for example, for bearings operating in a cold environment or those used in the air and air Space travel occur. Likewise, the modern lubricants under so-called clean room conditions should be used to avoid the pollution of the room by the abrasion or the consumption of lubricants. In addition, should be avoided in the application of modern lubricants that they evaporate and thus "leach", ie that they become solid after a short time use and no longer show any lubricating effect. On lubricants and special requirements in the application are made to the effect that the running surfaces of the bearings are not attacked by low friction, run the storage areas quiet, and long maturities are required without relubrication. Also, lubricants must withstand the effects of force such as centrifugal force, gravity and vibration.

An important parameter for a long service life of a grease-lubricated roller bearing in the high temperature range is, in addition to the upper service temperature according to DIN 51825, the noise behavior of the lubricant. A lubricating grease can stimulate vibrations in the rolling bearing during circulation participation (rolling over, rolling), which are "lubricant noises" in the frequency bands medium 300 to 1,800 Hz and high 1,800 to 10,000 Hz, compared to the bearing noise in the frequency band low at 50 to 300 Hz. The lubricant noise is superimposed by the noise peaks that occur during the rolling over of hard particles by the rolling elements in the form of shock pulses on the bearing ring. The noise behavior is evaluated according to the SKF-Bequiet method, which is based on the statistical evaluation of the noise peaks and the assignment to the noise classes BQ 1 to BQ4. As the noise class increases, the noise performance and life of the rolling bearing deteriorates (H. Werries, E. Paland, FVA Study on Low Noise Greases). University of Hannover 1994). Thus, 100% noise class BQ1 characterizes very good noise behavior and low percentages only in noise class BQ4 very poor noise behavior.

The better the noise behavior of a grease, the lower the vibrations of the bearing forced by the lubricant. This is equivalent to a low load on the bearing and leads to a longer service life of storage.

The use of ionic liquids, also referred to as IL (= lonic liquid) in the lubrication technique has been intensively studied in recent years, since the modification of cations or anions could offer a wide range of applications. Ionic liquids are so-called molten salts, which are preferably liquid at room temperature or by definition have a melting point <100 ° C. Known cation / anion combinations which lead to ionic liquids are, for example, dialkylimidazolium, pyridinium, ammonium and phosphonium, etc. with organic anions, such as sulfonates, imides, methides etc. as well as inorganic anions, such as halides and phosphates, etc., where any other combination of cations and anions is conceivable, with a low melting point can be achieved. Ionic liquids have an extremely low vapor pressure depending on their chemical structure, are non-combustible and often up over 260 ⁰ C thermally stable and beyond even lubricity.

WO 2006/077082 describes a method for sealing rotating shafts using mechanical seals and the use of ionic liquids as part of the sealing liquid for mechanical seals for sealing rotating shafts. These barrier fluids should serve to additionally seal rotating shafts. The known barrier fluids are water or oils whose behavior is to be improved by the use of ionic liquids with respect to the interaction with the environment of the machines with high tightness requirements. DE 10 2004 033 021 A1 describes the use of ionic liquids as hydraulic fluids, wherein the compressibility of liquid pressure transmission means is to be reduced and thus the energy transmission efficiency of hydraulic systems is to be improved.

From DE 10 2005 007 100 A1 a process or working machine is known in which an ionic liquid is used as the operating fluid. This ionic liquid is also used in the scope of use as a working liquid as a lubricating liquid, barrier liquid, sealing liquid, pressure transfer liquid and the like.

The use of liquid lubricants usually requires the use of elaborate seals. Greases themselves have a sealing effect. The use of complex seals is eliminated, you can work with simple lids or gaskets.

The object of the present invention is to provide a grease composition which meets the above requirements, is particularly applicable to high and low temperature conditions, has little or no vapor pressure and thus does not evaporate in use, and exhibits good noise performance, long run times and essentially causes no signs of wear of the bearing. In addition, the grease composition is intended to provide an oil separation suitable for the application.

This object is achieved according to the invention by a grease composition consisting of a mixture of a base oil mixture based on oils with viscosities customary for industrial lubricants (ISO VG 2 to ISO VG 1500), an ionic liquid or a mixture of several ionic liquids, a thickening agent for example, based on a polyurea compound and conventional additives, which can be used both at service temperatures of more than 120 ⁰ C to 260 ⁰ C and at low temperatures to -60 ⁰ C. The base oil mixture may be synthetic oil, a mineral oil and / or a virgin oil. These oils may be used singly or in combination depending on the use.

The synthetic oils are selected from an ester of an aliphatic or aromatic di-, tri- or tetracarboxylic acid with one or in mixture C ₇ - to C ₂₂ -alcohols, from a polyphenyl ether or alkylated diphenyl ether, from an ester of trimethylolpropane, pentaerythritol or dipentaerythritol with aliphatic C ₇ to C ₂₂ carboxylic acids, from C ₈ - dimer acid esters with C ₇ - to C ₂₂ alcohols, from complex esters, as individual components or in any desired mixture. Furthermore, the synthetic oil can be selected from poly-σ-olefins, alkylated naphthalenes, alkylated benzenes, polyglycols, silicone oils, perfluoropolyethers.

The mineral oils can be selected from paraffinic, naphthenic, aromatic hydrocracking oils; Gas to Liqud (GTL) - Liquids. GTL means gas-to-liquid process and describes a process for the production of fuel from natural gas. Natural gas is converted by steam reforming to synthesis gas, which is then converted by Fischer-Tropsch synthesis into fuels by means of catalysts. The catalysts and process condition control the fuel type, so whether gasoline, kerosene, diesel or oils are produced. In the same way coal can be used as a raw material according to the Coal-to-Liquid process (CTL) and biomass as a raw material in the Biomass-to-Liquid (BTL) process.

As native oils, animal / plant source triglycerides may be used which have been refined by known methods such as hydrogenation. The most preferred triglyceride oils are genetically modified high oleic acid triglyceride oils. Typical and genetically modified high oleic vegetable oils used herein are safflower oil, corn oil, rapeseed oil, sunflower oil, soybean oil, linseed oil, peanut oil, Lesquerella oil, Meadowfoam oil, and palm oil. In the case of the ionic liquids, as already stated above, the appropriate desired properties of the lubricant composition are achieved by suitable choice of cations and anions, such as increasing the service life and lubricating effect of the lubricant, adjusting the viscosity to improve temperature suitability, adjusting the electrical conductivity for broadening of the field of application. Suitable cations for ionic liquids have been found to be a phosphonium cation, an imidazolium cation, a pyridinium cation, or a pyrrolidinium cation, which can be combined with an anion containing fluorine and selected from bis (trifluoromethylsulfonyl) imide, bis (perfluoroalkylsulfonyl) imide, perfluoroalkylsulfonate, Tris (perfluoroalky) methides, bis (perfluoroalkyl) imides, bis (perfluoroaryl) imides, perfluoroarylperfluoroalkylsulphonylimides and tris (perfluoroalkyl) thfluorophosphate or with a halogen-free alkylsulfate anion.

Particularly preferred are ionic liquids with highly fluorinated anions, since these usually have high thermal stability. The ability to absorb water can be significantly reduced by such anions, for example when using the bis (trifluoromethylsulfonyl) anion.

Examples of such ILs are:

Butylmethylpyrrolidinium bis (trifluoromethylsulfonyl) imide (MBPimide), methylpropylpyrrolidinium bis (trifluoromethylsulfonyl) imide (MPPimide), 1-hexyl-3-methylimidazolium tris (perfluoroethyl) trifluorophosphate (HMIMPFET), 1-hexyl-3-methylimidazolium bis (trifluoromethylsulfonyl ) imide (HMIMimide), hexylmethylpyrrolidinium bis (trifluoromethylsulfonyl) imide (HMP),

Tetrabutylphosphonium tris (perfluoroethyl) trifluorophosphate (BuPPFET), N-hexylpyridinium bis (trifluoromethyl) sulfonylimide (Hpyimide), butylmethylpyrrolidinium tris (pentafluoroethyl) trifluorophosphate (MBPPFET), trihexyl (tetradecyl) phosphonium bis (trifluoromethylsulfonyl) imide (HPDimide), 1-ethyl-3-methylimidazolium ethylsulfate (EMIM ethyl sulfate),

1-Ethyl-3-methylimidazolium bis (trifluoromethylsulfonyl) imide (EMIMimide), 1-ethyl-2,3-dimethylimidazolium bis (trifluoromethylsulfonyl) imide (EMMIMimide), N-ethyl-3-methylpyridinium nonafluorobutanesulfonate (EMPyflat) The thickener is either a reaction product of a diisocyanate, preferably 2,4-diisocyanatotoluene, 2,6-diisocyanatotoluene, 4,4'-diisocyanatodiphenylmethane, 2,4'-disissocantodiphenylmethane, 4,4'-diisocyanatodiphenyl, 4,4 'Diisocyanato-3,3'-dimethyldiphenyl,4,4'-diisocyanato-3,3'-dimethylphenylmethane, which may be used singly or in combination with an amine of the general formula R ' ₂ NR, or a diamine of the general formula R ' ₂ NRN-R' ₂ , wherein R is an aryl, alkyl or alkylene radical having 2 to 22 carbon atoms and R 'is identical or different hydrogen, an alkyl, alkylene or aryl radical, or with mixtures of amines and Diamines or is selected from metal soaps, metal sulfonates, metal complex soaps, bentonite, silicate powder, polytetrafluoroethylene (PTFE), polyamide, polyimide.

In addition, the grease compositions according to the invention contain conventional additives against corrosion, oxidation and for protection against metal influences, which are used as chelate compounds, radical scavengers, UV stabilizers,

Reaction layer formers are present, and inorganic or organic solid lubricants such as polyimides, polytetrafluoroethylene (PTFE), graphite, metal oxides, boron nitride, molybdenum disulfide and phosphate. In particular, additives in the form of phosphorus and sulfur compounds, e.g. Zinkdialkyldithiophosphat, boric acid esters used as antiwear / extreme compressors, aromatic amino, phenols, sulfur compounds used as antioxidants, metal salts, esters, nitrogen-containing compounds, heterocyclic compounds used as corrosion inhibitors, glycerol mono- or di-ester as friction inhibitors and polyisobutylene, polymethacrylate as a viscosity improver used.

The grease compositions of the invention contain from 5 to 95% by weight of base oil blend, from 1 to 30% by weight of ionic liquid, from 3 to 50% by weight of thickener, from 0.1 to 10% by weight of additives.

In these grease compositions, the viscosity of the base oil is in the range of 1.98 to 1650 mrrrVs and that of the ionic liquid in the range of 1.98 to 1650 mm ² / s. In addition, the grease compositions drop points according to DIN ISO 2176 of> 180 ° C and are suitable according to DIN 51825 for service temperatures up to -60 ⁰ C.

The grease compositions are suitable for applications for upper service temperatures of more than 120 ⁰ C up to 260 ⁰ C and for low use temperatures of -60 ⁰ C according to DIN 51285. Also, they can be used at 51825 upper use temperatures of more than 180 ⁰ C and for low use temperatures of up to -60 ⁰ C according to DIN.

Surprisingly, the combination of the abovementioned constituents has resulted in a lubricant composition which has a longer service life by delaying the viscosity increase and thus delaying the laking / hardening of the lubricant as a result of the hardly existing evaporation of the ionic liquid. Moreover, by the use of ionic liquids, a lubricating grease composition can be obtained which is low in flammability, stable against oxidative and thermal influences, which can be used in a wide range in liquid form, which has a negligible vapor pressure and whose viscosity is appropriate can be adjusted.

Since urea fats are often used in rolling bearings where high temperatures prevail and long run times are achieved, it is necessary to adjust the fats for such applications because urea fats tend to harden under high temperatures. This may result in roller bearings or ball bearings with diameters of the inner ring of 100 mm or larger being insufficiently supplied with oil. Also, the described hardening can lead to lines for relubrication are impassable and thus no supply of fresh fat is possible or the hardened fat is no longer mixed with fresh fat. It is desirable that urea fats with higher oil separation and less tendency to harden at high temperatures can be used. Such improved products can, for example, in rolling bearings in the Corrugated board industry, the woodworking industry and in wheel bearings of commercial vehicles application.

In the case of metal soap greases, especially lithium soap greases and lithium complex soap greases, on the other hand, at higher temperatures the oil discharge is rather too large, so that, despite the use of seals, oil losses occur which limit the service life of the bearing.

It has now been found that an improvement of the disadvantages described above is achieved by the addition of ionic liquids. The following examples show that a lubricating grease composition containing the urea as a thickening agent and for lubricating roller bearings or ball bearings having inner rings of at least 100 mm in diameter, while avoiding the drawbacks of the known urea-based lubricating grease compositions. Also, such lubricating grease compositions can be used for relubrication of roller bearings or ball bearings with inner rings with diameters of at least 100 mm.

As particularly advantageous embodiments of the grease composition according to the present invention, the following compositions have been found.

Lubricating grease compositions according to claim 1 consisting of 79% by weight of poly-σ-olefin as base oil, 17% by weight of lithium as a thickener, 4% by weight of additives and 1 to 30% by weight of butylmethylpyrrolidinium bis (trifluoromethylsulfonyl) imide as ionic liquid , A grease composition consisting of 73.5% by weight of poly-σ-olefin, 4.5% by weight of urea thickener and 15% by weight of lithium complex soap thickener, 3% by weight of additives and 4% by weight of solid lubricants, into which additional 1 to 5% by weight % Ionic liquids are incorporated, wherein the ionic liquid is selected from trihexyl (tetradecyl) phosphonium bis (trifluoromethylsulfonyl) imide or N-ethyl-3-methylpyridinium nonafluorobutanesulfonate.

Also, lubricating grease compositions consisting of 85% by weight of ester mixture, 7.5% by weight of urea thickener, 5% by weight of additive mixture and 2.5 to 10% by weight of 1-ethyl-3-methylimidazolium bis- (trifluoromethylsulfonyl) imide advantageous in the application according to the present invention.

Also grease compositions consisting of 84% by weight of synthetic esters, 14% by weight of urea thickener, 2% by weight of additives and 1 to 3% by weight of 1-ethyl-3-methylimidazolium ethylsulfate can be used according to the invention.

A grease composition which may consist of 76% by weight of a mixture of synthetic esters and poly-σ-olefins, 15% by weight of urea thickener, 9% by weight of additives and additionally 1 to 10% by weight of butylmethylpyrrolidinium bis (trifluoromethylsulfonyl) imide Application come.

The lubricant compositions of the invention are obtained either by mixing the di- and / or polyurea-thickened base oil with the ionic liquid and then homogenizing via a high-pressure homogenizer and / or three-roll mill, or by mixing the base oil with the ionic liquid and thickened in situ in this mixture by synthesis of the poly- or diurea compound and then homogenized by means of a high-pressure homogenizer and / or three-roll mill.

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

Examples

Unless otherwise specified in the examples, the percentages are% by weight. By adding the ionic liquid, the percentage of the remaining base oil, unless otherwise stated, correspondingly reduced.

example 1

To prepare a grease composition 77 wt .-% of a mixture of trimellitic / pyromellitic acid ester as a base oil, 10 wt .-% MPBimid as ionic liquid, 8 wt .-% poly or diurea as thickener and 5 wt .-% corrosion inhibitor, antioxidant and Wear protection agents mixed as additives. After the in situ production of the thickener, the ionic liquids are mixed into base oil and homogenized by means of high-pressure homogenizers, three-roll mill or other suitable methods. First, a noise test according to DIN ISO 2137 was carried out with the grease composition thus obtained, and the results are shown in Table 1.

Table 1

SKF - Fat Noise Test BeQuiet +

Bequiet + exam

Grease class: GN 1

0% BQ1, 26% BQ2, 82% BQ3, 99% BQ4

The upper service temperature was according to DIN 51825 on the FAG FE-9 Wälzlagerprüfmaschine, FAG FE 9 test at 180 ° C, 6000 rpm, 1500 N, Installation A: L 10 = 73 h L 50 = 222 h ß = 1, 7, this Results show that the grease compositions according to the invention not only meet the requirements of noise testing and the DIN standards for rolling bearing greases, but far exceed these values.

Example 2

To prepare a grease composition are added to a grease consisting of 79% by weight of a mixture of poly-αr-olefins as base oil, 17% by weight of a lithium soap as thickener, 4% by weight of additives are additionally 10 and 30% by weight of MPBimid Ionian Liquid added. The ionic liquid is cold after the in situ production of the lithium soap grease added to the base oil, stirred and rolled homogeneously.

Table 2

Table 2 shows the significant reduction of oil separation by the addition of

Ionic fluid preserving the other parameters tested.

The separated oil (FTMS standard) was identified as base oil, i. it does not separate any ionic liquid.

After the above-described basic recipe for a lithium soap grease according to Example 2, further experiments were carried out with smaller amounts of ionic liquid, the results are shown in Table 3.

Table 3

Even when using 1 to 5% by weight of ionic liquid, a reduced oil separation is also evident, even if the test time is extended to 30 hours.

Example 3

In this example, a standard grease containing 10% MBPimide added to a rolling bearing grease consisting of a synthetic hydrocarbon, a synthetic ester, an aromatic diisocyanate, aliphatic monoamines is prepared in a ROF rolling bearing grease testing machine. This test determines the life of the grease composition under study and determines the upper service temperatures of greases in rolling bearings at high speeds and, by default, low axial and radial loads. The test bearing was a deep groove ball bearing 6204-2Z-C3Λ / M104 was used, which was subjected to a load of 100 N in the axial load and 200 N in the radial load, a speed of 180001 / min, a temperature of 160 ⁰ C, and with a capacity of 1, 5 cm ^{3 was} loaded. It was found that the grease composition without IL had an L ₅₀ value of 186 hours and the grease composition had an L ₅₀ value of 717 hours. This shows the significant improvement in the life of an ionic liquid grease composition.

Example 4

In this example, the VKA welding force is determined according to DIN 51350. For this purpose, a rolling bearing grease consisting of synthetic ester, perfluoropolyether (PFPE), aromatic diisocyanate and a mixture of aliphatic and aromatic amines was used. The following

Grease compositions were then subjected to the VKA Welding Test.

Grease compositions, these are NLGI 2-3 greases:

Fat 1: Standard with perfluoropolyether Fat 2: Standard without perfluoropolyether with 2.5% EMIMimide Fat 3: Standard without perfluoropolyether with 5% EMIMimide Fat 4: Standard without perfluoropolyether with 7.5% EMIMimide Fat 5: standard without perfluoropolyether with 10% EMIMimide

Table 4

The comparison of the VKA values shows that with an addition of more than 2.5% of ionic liquid a better VKA value is achieved.

Table 5

In addition, a better VKA value is shown with equally good noise levels with the addition of 10% ionic liquid.

The greases were also subjected to a FE 9 rolling bearing grease test, which determines the service life of the greases tested and determines the upper service temperature of greases in rolling bearings at medium speeds and medium axial loads. The bearing used was a FAG special bearing 529689 H 109 (this corresponds to an angular ball bearing 7206 B with steel cage), with a JP2 cage at a speed of 6000 1 / min, an axial load of 1500 N at a temperature of 200 ^° C. and a capacity of 2 cm ³ used. The greases tested and the results of the L10 and L50 values are shown in Table 6. Table 6

The table shows that by the addition of ionic liquids, the fats have longer run times, as can be seen from the comparison with the values determined for fat 1 with perfluoropolyether without ionic liquids.

Another grease composition was subjected to a FAG FE 9 test, to which fat without PFPE was added 10% HDPimide (Grease 8). The following run times were obtained Li ₀ : 66 h, L ₅₀ : 101 h and / ?: 4.4. These results show that the grease compositions according to the invention meet the requirements for rolling bearing greases according to DIN standards for a service temperature up to 200 ⁰ C.

Example 5

In this example, the VKA welding force is determined according to DIN 51350. For this purpose, a rolling bearing grease consisting of synthetic ester, aromatic diisocyanate and aliphatic amines was used as the standard composition. The following grease compositions were then subjected to the VKA Welding Test.

Grease compositions, these are NLGI 2-3 greases: Grease 1: standard without IL Fat 2: Standard with addition of 5% EMIMimide, (oil substitute) Fat 3: Standard with addition of 10% EMIMimide, (oil substitute)

Table 7

Table 7 shows that the welding force is improved, better VKA values are obtained with use of IL in the grease.

Table 8

Better VKA value with the same good noise level (use 10% IL):

In addition, it was examined whether the addition of ionic liquids can prevent the hardening of fats under temperature load.

At a temperature load of 160 ⁰ C, a so-called "Aluschälchentest" was used. For this purpose, first the viscosity of the not yet loaded fat is measured. In a small aluminum bowl, diameter approx. 50 mm, height approx. 15 mm, the fat to be tested is coated as homogeneously and smoothly as possible up to a% of the bowl height. Then the bowl is closed with the appropriate lid. The closed dish is then placed on a baking tray and loaded in an oven at elevated temperature. In a weekly rhythm, the viscosity of the fat is measured. The apparent dynamic viscosity is measured at 300 s ^-1 , 25 ^° C. The following grease compositions were subjected to this test: Fat 1: Standard recipe without IL Fat 5: Addition of 1% EMIM ethylsulfate Fat 6: Addition of 3% EMIM ethylsulfate Fat 7: Addition of 5% EMIM ethylsulfate

Table 9

The values of the apparent dynamic viscosity are given in mPas.

With the addition of 1% EMIM ethylsulfat the fat is softer, with 3% the fat is very inhomogeneous (not measurable) and with 5% totally "fallen apart" (not measurable).

It can be clearly seen that the addition of 1% EMIM ethyl sulfate leaves the material softer under temperature load. For additions greater than 1% IL, no improvement in temperature exposure can be seen.

Example 6

In this example, the improvement of wheel bearing greases in the addition of

Ionic liquids examined. In particular wheel bearing greases for trucks are subject to high demands both thermally and in terms of the load. A particularly high thermal load is created when the vehicles have to be braked constantly during downhill, for example, mountain passes. To simulate this stress FE 8 rolling bearing tests are performed, which are characterized by a periodic temperature change.

As a base grease for these studies, a composition of a poly-σ-olefin, an aromatic diisocyanate, a mixture of aliphatic and aromatic amines and a lithium complex soap (standard) is used.

The following grease compositions were used:

Fat 1: standard recipe

Fat 2: Standard plus 5% HDPimide These grease compositions were subjected to the following tests shown in Table 10.

Table 10

The fat to which 5% HDPimide was added showed a higher oil separation.

To investigate the hardening, the above-described covered alchohol test was carried out.

The viscosity measurements were carried out at 160 ^° C., the values are given in mPas.

Table n

For all samples, the apparent viscosity can be measured; the standard fat appears to be dryer in appearance than the fat with IL.

The pattern with IL has a viscosity drop and is softer than the pattern without IL, which gets harder.

This leads to runtime extension, for example in FE 8 rolling bearing examinations. In these investigations, the friction torque and temperature profile in the bearing as well as the wear of the rolling bearing components according to DIN 51819 are determined. The periodically changing temperature changes between 13O ⁰ C, this corresponds to the normal operation and 170 ⁰ C, this corresponds to a departure from the mountain fun. In the composition designated with fat 1 without IL showed a high wear and a short run time of 215 hours, already at a second tempering phase of 170 ⁰ C, the test had to be stopped, the material generated so much self-heat that the fan had to be switched on.

The tests with the grease composition designated as grease 2 plus 5% HDPimide showed less wear and a longer running time of 377 hours, it was possible to run 5 cycles with a temperature of 17O ⁰ C. The testing machine was switched off deliberately, another operation would have been possible. The material led only to a small self-heating, it had to be heated.

Further investigations were carried out with the following grease compositions, the results are shown in Tables 12 and 13.

Fat 1: Standard recipe (Example 6) without IL

Fat 3: Standard plus 1% HDPimide

Fat 4: Standard plus 2% HDPimide

Fat 5: Standard plus 3% HDPimide Fat 6: Standard plus 1% N-ethyl-3-methylpyridinium nonafluorobutanesulfonate

Fat 7: Standard plus 2% N-ethyl-3-methylpyridinium nonafluorobutanesulfonate

Fat 8: Standard plus 3% N-ethyl-3-methylpyridinium nonafluorobutanesulfonate

Table 12

The patterns with IL have increased oil deposits. Thus, the amount of oil separation can be adjusted by the type and amount of the ionic liquid used. Table 13

Viscosity measurements, load at 160 ^° C; Values are given in mPas:

The example shows that the performance of a wheel bearing grease for trucks can be significantly increased by ionic liquids.

The above examples demonstrate the beneficial effect of adding ionic liquids to industrial lubricants based oils.

Claims

Grease composition patent claims

1. grease composition consisting of a mixture of (a) 5 to 95% by weight base oil based on oils with

Industrial lubricants usual viscosity, which consists of an ester of an aromatic or aliphatic di-, tri- or tetracarboxylic acid with one or in mixture C ₇ - to C∞ alcohols, from a polyphenyl ether or alkylated diphenyl ether, from an ester of trimethylolpropane, pentaerythritol or dipentaerythritol with aliphatic C ₇ to

C22 carboxylic acids, of C ₈ -Dimersäureestem with C ₇ - to C ₂₂ alcohols, from Komplexestem, exists as individual components or in any mixture, or is selected from poly-σ-olefins, alkylated naphthalenes, alkylated benzenes, polyglycols, silicone oils, Perfluoropolyethers, (b) 1 to 30% by weight of ionic liquid or a mixture of several ionic liquids containing as cation a Phosphoniumkation, Imidazoliumkation, Pyridiniumkation or Pyrrolidiniumkation and their anion contains fluorine and is selected from the group consisting of bis (trifluromethylsulfonyl) imide , Bis (perfluoroalkylsulfonyl) imide, perfluoroalkylsulfonate, tris (perfluoroalky) methides, bis (perfluoroalkyl) imides,

Bis (perfluoroaryl) imides, perfluoroarylperfluoroalkylsulphonylimides and tris (perfluoroalkyl) trifluorophosphate or their anion consists of a halogen-free alkylsulfate, (c) from 3 to 50% by weight of thickener selected from the group consisting of a reaction product of a diisocyanate, preferably 2,4-

Diisocyanatotoluene, 2,6-diisocyanatotoluene, 4,4'-diisocyanatodiphenylmethane,

2,4'-diisocyanate diphenylmethane, 4,4'-diisocyanatodiphenyl, 4,4'-

Diisocyanato-3,3'-dimethyl diphenyl, 4,4'-diisocyanato-3,3 ^I -dimethylphenyl- methane, individually or may be used in combination with an amine of the general formula R ^ NR ₁ or a diamine of the general formula R ^ NRNR ^, wherein R is an aryl, alkyl or alkylene radical having 2 to 22 carbon atoms and R ^{1 is} identical or different

Is hydrogen, an alkyl, alkylene or aryl radical, or with a mixture of amines and diamines or metal soaps, metal sulfonates, metal complex soaps, bentonite, silicate powder, polytetrafluoroethylene (PTFE), polyamide, polyimide, and

(d) 0.1 to 10% by weight of conventional additives, singly or in combination, selected from the group consisting of corrosion inhibitors, antioxidants, anti-wear agents, friction reducing agents, agents for protection against metal influences, UV

Stabilizers, inorganic or organic solid lubricants selected from polyimide, polytetrafluoroethylene (PTFE), graphite, metal oxides, boron nitride, molybdenum disulfide and phosphate.

A grease composition according to claim 1 wherein the ionic liquid is selected from the group consisting of butyl-methylpyrrolidinium bis (trifluoromethylsulfonyl) imide, methylpropylpyrrolidinium bis (trifluoromethylsulfonyl) imide, 1-hexyl-3-methylimidazolium tris (perfluoroethyl) trifluorophoshate, 1- hexyl-3-methylimidazolium-bis imide (trifluoromethylsulfonyl)

Hexylmethylpyrrolidinium bis (trifluoromethylsulfonyl) imide, tetrabutylphosphonium tris (perfluoroethyl) trifluorophosphate, N-hexylpyridinium bis (trifluoromethyl) sulfonyl imide, butylmethylpyrrolidinium tris (pentafluoroethyl) trifluorophosphate, Trihexyl etradecyOphosphonium bis (rifluromethylsulfonyimicyl), 1-ethyl-3-methylimidazolium ethylsulfate, 1-ethyl-3-methylimidazolium bis (trifluoromethylsulfonyl) imide, 1-ethyl-2,3-dimethylimidazolium bis (trifluoromethylsulfonyl) imide, N-ethyl-2- methylpyridinium nona-fluorbutansulfonat.

3. A grease composition according to claim 1 or 2 consisting of 79% by weight of poly-σ-olefin as a base oil, 17% by weight of lithium as a thickening agent, 4% by weight of additives and additionally 1 to 30% by weight of butyl methylpyrrolidinium bis (trifluoromethylsulfonyl ) imid as

Ionic liquid.

4. The grease composition according to claim 1 consisting of 73.5% by weight of poly-σ-olefin, 4.5% by weight of urea thickener, 15% by weight of lithium complex soap thickener, 3% by weight of additives, 4% by weight

Solid lubricants and 1 to 5% by weight of ionic liquids, wherein the ionic liquid is trihexyl (tetradecyl) phosphonium bis (trifluoromethylsulfonyl) imide or N-ethyl-3-methylpyridinium nonafluorobutanesulfonate.

5. A grease composition according to claim 1, consisting of 85% by weight of ester mixture, 7.5% by weight of urea thickener, 5% by weight of additives and 2.5 to 10% by weight of 1-ethyl-3-methylimidazolium bis (trifluoromethylsulfonyl) imide ,

6. A grease composition according to claim 1, consisting of 84% by weight of synthetic ester, 14% by weight of urea thickener, 2% by weight of additives and 1 to 3% by weight of 1-ethyl-3-methylimidazolium ethylsulfate.

A grease composition according to claim 1, consisting of 76% by weight of a mixture of synthetic esters and polyalfaolefins, 15% by weight of urea thickener, 9% by weight of additives and 1 to 10% by weight of butylmethylpyrrolidinium bis (trifluoromethylsulfonyl) imide.

8. A grease composition according to any one of claims 1 to 7, wherein the viscosity of the base oil in the range of 1, 98 to 1650 mπrYs and the

Ionic liquid is in the range of 1, 98 to 1650 mm ² / s.

9. grease composition according to one of claims 1 to 7, wherein the dropping points according to DIN ISO 2176 are greater than> 180 ° C and are suitable according to DIN 51825 for use temperatures up to -60 ⁰ C.

10. A process for the preparation of the grease composition according to any one of claims 1 to 9, characterized in that it is obtained either by the thickened with the thickener base oil is mixed with the ionic liquid and then over a

High-pressure homogenizer and / or three-roll mill is homogenized or by the base oil is mixed with the ionic liquid and thickened in this mixture by synthesis of the thickener and then homogenized via a high-pressure homogenizer, three-roll mill and / or other suitable method.

11. A grease composition according to any one of claims 1 to 10 for applications for upper service temperatures of more than 120 ⁰ C up to 260 ° C and for low service temperatures up to -60 ° C according to DIN 51825th

12. grease composition according to one of claims 1 to 11 for applications for upper service temperatures of more than 180 ⁰ C up to 260 ⁰ C and for low use temperatures up to -60 ⁰ C according to DIN 51825th

13. A grease composition according to claim 1, which contains urea as a thickener and is used for lubricating roller bearings or ball bearings with inner rings with diameters of at least 100 mm.

14, grease composition according to claim 1, which contains urea and is used for relubrication of roller bearings or ball bearings with inner rings with diameters of at least 100 mm.