EP3692120A1

EP3692120A1 - Hybrid grease with low friction coefficients and high wearing protection

Info

Publication number: EP3692120A1
Application number: EP19742289.2A
Authority: EP
Inventors: Reiner Schmitz; Martin Wimmer; Stefan Seemeyer
Original assignee: Klueber Lubrication Muenchen SE and Co KG
Current assignee: Klueber Lubrication Muenchen GmbH and Co KG
Priority date: 2018-07-24
Filing date: 2019-07-12
Publication date: 2020-08-12
Anticipated expiration: 2039-07-12
Also published as: JP2021508750A; BR112020011943A2; CN111770979B; KR102370955B1; EP3692120B1; US20210171856A1; JP7090711B2; WO2020020476A1; US11274263B2; KR20200079512A; CN111770979A; DE102018005835A1

Abstract

The invention relates to the provision of a new type of hybrid grease which has low friction coefficients and high wearing protection and can be used in a wide temperature range. The new type of hybrid grease is based on a combination of grease on the basis of a silicon oil in conjunction with grease on the basis of synthetic hydrocarbon oils, mineral oils or polyglycols. The new type of hybrid grease can especially be used to lubricate joints in vehicle parts of the plastic-steel pairing type.

Description

Hybrid grease with low friction and high wear protection

description

The present invention relates to the provision of a new hybrid grease with low coefficients of friction and high wear protection, which can be used in a wide temperature range. The new hybrid grease is based on a combination of a grease based on a silicone oil in combination with a grease based on synthetic hydrocarbon oils, mineral oils or polyglycols. In particular, the new hybrid grease can be used to lubricate joints in vehicle parts based on plastic-steel combinations, and also for use in actuators that are increasingly used in vehicles, such as in brakes, brake boosters, steering assistance (EPS) and window regulators ,

Particularly low coefficients of friction, which can also be maintained very consistently over a wide temperature range, are achieved with a lubricant based on silicone oil. A high base oil viscosity is required to further improve the coefficient of friction and stick-slip behavior. Silicone greases, especially those based on polydimethysiloxane, have a very high viscosity index and a low pour point. This enables the properties described above to be achieved. However, the grease compositions based on silicone oils show weaknesses in wear protection, especially in highly stressed applications, such as, for example, highly tensioned chassis joints. A high level of wear protection is achieved with greases based on mineral oils, synthetic hydrocarbons such as PAO, esters, polyglycol or PFPE. To cover a wide temperature range, base oils with the highest possible viscosity index and a low pour point are required. PFPE as a base oil is out of the question for many applications due to the high costs. Even with the current developments based on synthetic hydrocarbons, eg m-PAOs (metallocene PAO), this goal can only be achieved to a limited extent. In order to achieve a low coefficient of friction with systems based on synthetic hydrocarbons, additives such as PTFE are required, but this leads to very high raw material costs.

Lubricant compositions are known from WO 2104/028632 A1 which contain a silicone oil-free oil and a silicone oil as base oil, the silicone oil being an oil-soluble oil and being selected from ethyl silicone, octyl silicone. Lithium soaps are also mentioned as thickeners.

US 4,251,431 B describes the production of oils based on PFPE with methylpolysiloxanes as hybrid fats, the two oil phases being insoluble.

EP 0 657 524 B1 also describes the mixture of PFPE oils with another PFPE-insoluble oil component.

WO 2013/010851 A1 discloses a lubricant composition which has two components, a low-viscosity component together with a high-viscosity component which can be separated from the low-viscosity component at low temperatures and becomes uniform at high temperatures.

The known hybrid greases refer to the mixing of PFPE greases or oils with others in PFPE-free greases as well as to immiscible compositions. The present invention therefore aims to provide a lubricant composition which meets the above requirements, in particular can be used in a further temperature range from -50 ° C. to + 160 ° C. and which has low coefficients of friction and long running times and essentially no signs of wear the components.

For this purpose, according to the invention, a hybrid fat consisting of a mixture of a fat based on a silicone oil with a fat or oil based on a synthetic hydrocarbon oil, mineral oil or polyglycol oil and a thickener and conventional additives is provided. It is crucial that the two base oils or oil phases cannot be mixed.

In "Synthetic Lubricants and High Performance Functional fluids" (Editor RL Shubkin), Marcel Dekker Inc, New York, Basel, Hong Kong 1993, ISBN 0-8247-8715-3 you will find information on the typical PAO (pages 1 to 40) , on silicone oils (pp. 183 to 203) and polyglycols (pp. 101 to 123). Metallocene-catalyzed PAO were, for example, given by ExxonMobil during a lecture ("The influence of Molecular Structure on the Properties of Polyalphaolefins", authors Bruce Harrington, Sandy Reid-Peters) at the 19th International Tribology Colloquium in Esslingen (January 21 to 23, 2014) ) presented.

In Ullmann's Encyclopedia of Technical Chemistry, 4th, revised and extended editions, Verlag Chemie, 1981, Volume 20, in the article “Lubricant and Related Products” (pages 457 to 671) by D. Klamman, you can also find information on silicone oils (p. 523 to 525). The viscosity of the oils can be from 18 mm ² / s to 20,000 mm ² / s at 40 ° C.

It is usually not possible to mix a silicone oil with a synthetic hydrocarbon oil. Surprisingly, however, fats can be mixed that are based on immiscible base oils, such as silicone oil Polydimethysiloxane and as a synthetic hydrocarbon, for example PAO. These can be mixed so that a homogeneous lubricant is created. It is also possible to prepare a batch with silicone oil as the base oil and thickener and to add the synthetic hydrocarbon oil as a mixing component analogously to an additive. It is also possible to prepare a batch with synthetic hydrocarbon oil as the base oil and thickener and to add only the silicone oil as a mixing component analogous to an additive. The mixture can be produced with agitators as they correspond to the state of the art in the production of greases. After the mixing, a subsequent homogenization process step can take place, for example by means of a grinder (colloid mill), rolling mill or high-pressure homogenizer.

The lubricant thus produced shows all the properties required and desired above.

The silicone oil is selected from the group consisting of polydimethylsiloxane, polyphenylmethylsiloxane or mixtures of both oils. The synthetic hydrocarbon oil is selected from the group consisting of PAO, blends of PAO and olefin copolymers, blends of PAO and polyisobutylene. The thickener is selected from the group of non-soap thickeners such as ureas and soap thickeners such as complex and single soap thickeners, particularly preferred are lithium 12-hydroxystearate and lithium stearate.

Furthermore, conventional additives such as antioxidants, anti-corrosion agents and a solid lubricant can be contained in the hybrid grease according to the invention.

For the hybrid fat according to the invention

(A) 10 to 50% by weight of a fat based on a synthetic

Hydrocarbon oil, mineral oil or polyglycol containing 50 to 90% by weight Base oil selected from synthetic hydrocarbon oil, PAO, mineral oil or polyglycol, 10 to 25% by weight thickener, 0 to 10% by weight additives with

(B) 50 to 90% by weight of a silicone fat containing 70 to 90% by weight of silicone oil, 5 to 30% by weight of thickener and up to 0 to 10% by weight of additives.

Component (A) can optionally contain 0 to 50% by weight of solid lubricant. Solid lubricants can be, for example, PTFE, graphite, molybdenum disulfide, melamine cyanurate and mixtures thereof.

Are particularly preferred for the hybrid fat according to the invention

(A) 10 to 20% by weight of a fat containing 70 to 90% by weight of base oil, selected from synthetic hydrocarbon oil, mineral oil or polyglycol, 10 to 20% by weight of thickener, 1 to 7% by weight of additives

(B) 80 to 90% by weight of a silicone fat containing 70 to 80% by weight of polydimethylsiloxane, up to 30% by weight of thickener and 1 to 10% by weight of additives.

A hybrid fat is particularly preferred, in which PAO, mPAO, ethylene, LAO copolymers are used as synthetic hydrocarbons.

Figure 1 shows the structure of a device for determining the coefficients of friction based on a torque test in a ball joint.

Figure 2 shows an example of the time course of the measurement of the device in Figure 1.

Figure 3 shows the device for determining wear protection based on a wear protection test in a ball joint. The invention is illustrated by the following examples.

Examples

production:

A state-of-the-art manufacturing process for greases is used.

The base oil or part of the base oil or oil mixture is placed in a suitable heatable container with an agitator, as used in the prior art for the production of lubricating greases. This is where the thickener is produced, such as the neutralization of stearic acid or 12-OH stearic acid with lithium hydroxide and subsequent heating phase to remove the water and to form the thickener structure. Peak temperatures of up to 210 ° C can be reached in order to melt the soap thickener completely and then adjust the morphology of the thickener by targeted cooling. In the subsequent cooling phase, the additives are added and distributed homogeneously. It is also possible to prepare a batch with silicone oil as the base oil and thickener and to add the synthetic hydrocarbon oil as a mixing component analogously to an additive. It is also possible to prepare a batch with synthetic hydrocarbon oil as the base oil and thickener and to add only the silicone oil as a mixing component analogous to an additive. This is followed by a homogenization process e.g. via a rolling mill or a colloid mill or a high-pressure homogenizer as is customary in the prior art for the production of lubricating greases.

The fat components (A) and (B) shown in Table 1 were prepared according to the procedure described above. All figures are in% by weight. Table 1

Hybrid fats:

The mixture of the two greases can be produced with agitators as they correspond to the state of the art in the production of lubricating greases. It is also possible to produce a batch with silicone oil as the base oil and thickener and the synthetic hydrocarbon oil as a mixing component analogous to an additive admit. It is also possible to prepare a batch with synthetic hydrocarbon oil as the base oil and thickener and to add only the silicone oil as a mixing component analogous to an additive. After the mixing, a subsequent homogenization process step can take place, for example, using a grinding mill (colloid mill), rolling mill or high-pressure homogenizer.

According to this process, the hybrid fats according to the invention were produced from components (A) and (B), which are shown in Table 2. All figures are in% by weight.

Table 2

Determination of the coefficients of friction

The test method described below was used to determine the coefficients of friction based on a torque test in a ball joint. The structure of the test system is shown in Figure 1. Ball joints were used, as are standard in the chassis of vehicles. The balls are made of steel with a diameter of 23 mm. The steel ball is enclosed in a plastic shell made of POM (polyoxymethylene). The lubricant is introduced between the plastic shell and the steel ball. Then the POM shell with the ball is inserted in a form-fitting manner. The housing is pressed in such a way that a certain force is exerted on the shell and ball system. In the present example, the surface pressure is approx. 1 N / mm ² .

Table 3 shows the results of the determination of the friction values using a torque test.

Table 3

Compared to greases based on synthetic hydrocarbons, the loosening and running moments could be positively influenced by hybridization. The low loosening torques and running torques of the silicone grease over the entire temperature range could be achieved particularly advantageously with the hybrid greases B and C and in some cases even exceeded, ie reduced.

Determination of wear protection

The wear test was carried out in a ball joint.

The described ball joint is loaded by a device with a load of 3240N. The device is movably supported so that the ball can be tilted in the POM shell. The tilting movement is carried out with a deflection of 3 ° and a frequency of 15 Hz. The movement is stopped at regular intervals and the play caused by wear and tear is determined by relieving and reversing the load.

The structure of the wear protection test equipment is shown in Figure 3.

The result of the wear test is shown in Table 4.

The wear path of the joint was evaluated after 1.1 million load changes

Table 4

Compared to silicone grease, the wear values could be positively influenced by hybridization. With the hybrid greases B in particular, a very good level of wear could be achieved.

Claims

claims

1. Comprehensive hybrid fat

(A) 10 to 50% by weight of a fat based on a synthetic hydrocarbon oil, mineral oil or polyglycol, containing 50 to 90% by weight of base oil selected from synthetic hydrocarbon oil, PAO, mineral oil or polyglycol, 10 to 25% by weight Thickeners, 0 to 10 wt .-% additives and

(B) 50 to 90% by weight of a silicone fat containing 70 to 90% by weight of silicone oil selected from the group consisting of polydimethylsiloxane, polyphenylmethylsiloxane or mixtures thereof, 5 to 30% by weight of thickener and 0 to 10% by weight % Additives.

2. Hybrid fat according to claim 1 in particular comprising

(A) 10 to 20% by weight of a fat based on a synthetic hydrocarbon oil, mineral oil or polyglycol containing 70 to 80% by weight of base oil selected from synthetic hydrocarbon oil, PAO, mineral oil or polyglycol, 10 to 20% by weight of thickener , 1 to 7 wt .-% additives and

(B) 80 to 90% by weight of a silicone grease containing 70 to 80% by weight silicone oil selected from the group consisting of polydimethylsiloxane, polyphenylmethylsiloxane or mixtures thereof, 10 to 30% by weight thickener and 1 to 10% by weight additives.

3. Hybrid fat according to claim 1 or 2, which further contains in component (A) 0 to 50 wt .-% of a solid lubricant.

4. Hybrid fat according to one of claims 1 to 3, which contains as the synthetic hydrocarbon oil an oil selected from the group consisting of PAO, mixtures of PAO and olefin copolymers, mixtures of PAO and polyisobutylene.

5. Use of the hybrid grease according to one of claims 1 to 4 for the lubrication of joints in the vehicle sector.

6. Use of the hybrid grease according to claim 5 for the lubrication of joints on the basis of plastic / steel pairings.

7. Use of the hybrid grease according to one of claims 1 to 4 for the lubrication of actuators as used in vehicles for steering assistance (EPS), brake actuators, brake boosters. Window regulators are used.

8. Use of the hybrid fat according to one of claims 1 to 4, wherein the hybrid fat is produced by mixing the two different fats and subsequent homogenization.

9. Use of the hybrid fat according to one of claims 1 to 4, wherein the hybrid fat is produced by producing a fat with one of the oils, into which the second insoluble oil component is subsequently added.