EP3372660B1 - High temperature lubricants - Google Patents

Description

Based on estolides, additives and fully hydrogenated polyisobutylene or a mixture of hydrogenated and fully hydrogenated polyisobutylene. The invention also relates to the use of this high-temperature grease for continuous use temperatures of up to 250 ° C.

In addition to the lubricating effect, the lubricants have to fulfill a number of other tasks: They have to cool, reduce friction, wear and power transmission, protect against corrosion and at the same time have a sealing effect. In addition, the high-temperature greases should be quiet. Conventional lubricants are not suitable for high-temperature applications because they are destroyed at high temperatures, for example via oxidation and / or thermal decomposition reactions and polymerizations, and their lubricating properties are severely restricted. During decomposition reactions, the lubricant is split into low-molecular volatile components. Their evaporation leads to undesirable changes in viscosity, loss of oil and excessive vapor formation. This results in a loss of the lubricating effect. They also lose through polymerization Lubricants their lubricating effect due to the formation of insoluble polymerisation products.

Removing this contamination increases maintenance work and produces chemical waste that is laborious to dispose of. Due to the increased cleaning and maintenance work, the downtimes increase. Overall, the use of unsuitable lubricants in high-temperature applications leads to higher costs, since the tools become dirty and there is a higher demand for lubricants. In addition, the product quality decreases.

Synthetic esters are often used as base oils for high-temperature applications because they have very good oxidative, hydrolytic and thermal stability.

In order to meet the diverse requirements of high-temperature applications, the lubricants must have, among other things, high stability, low coefficients of friction and high wear resistance. In order to be able to guarantee uniform lubrication even at high temperatures, a liquid lubricating film must remain between metal parts during the entire processing process. For this reason, the lubricant must only evaporate a little at the maximum processing temperature, form few residues and form as few cracking residues as possible.

High temperatures often occur when used in chains, roller and plain bearings, in vehicle technology, conveyor technology, mechanical engineering, office technology and in industrial systems and machines, but also in the areas of household machines and entertainment electronics.

In roller and plain bearings, lubricants ensure that a separating, load-transferring lubricating film is built up between parts sliding or rolling on each other. This ensures that the metallic surfaces do not touch each other and therefore no wear occurs. The lubricants must therefore meet high requirements. This includes extreme Operating conditions such as very high or very low speeds, high temperatures caused by high speeds or external heating, very low temperatures, for example with bearings that work in a cold environment or that occur during use in the aerospace industry. Modern lubricants should also be able to be used under so-called clean room conditions in order to avoid room pollution from abrasion or the consumption of lubricants. In addition, when using modern lubricants, it should be avoided that they evaporate and thus "clog", ie that they become solid after a short application and no longer show any lubricating effect. Special requirements are also placed on lubricants when they are used in such a way that the running surfaces of the bearings are not attacked by low friction, the bearing surfaces run quietly, and long running times are achieved without relubrication. Lubricants also have to withstand the effects of forces such as centrifugal force, gravity and vibrations.

• GNX: etwas schlechter als GN1 (sehr schlechtes Geräuschverhalten)
• GN1: >95% aller Peaks sind <=40 µm/s (schlechtes Geräuschverhalten)
• GN2: >95% aller Peaks sind <=20 µm/s; > 98% aller Peaks sind <= 40 µm/s (mittleres Geräuschverhalten)
• GN3: >95% aller Peaks sind <=10 µm/s; > 98% aller Peaks sind <= 20 µm/s; > 100% aller Peaks sind <= 40 µm/s (gutes Geräuschverhalten)
• GN4: >95% aller Peaks sind <= 5 µm/s; > 98% aller Peaks sind <= 10 µm/s; > 100% aller Peaks sind <= 20 µm/s (sehr gutes Geräuschverhalten)

Je besser das Geräuschverhalten eines Schmierfettes, desto geringer sind die durch den Schmierstoff erzwungenen Schwingungen des Lagers. Dies ist gleichbedeutend mit einer geringen Belastung des Lagers und führt zu einer längeren Funktionsdauer der Lagerung.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, the noise behavior of the lubricant. A lubricating grease can stimulate vibrations in the rolling bearing when it participates in circulation (rolling over, flexing), which are "lubricant noises" in the medium 300 to 1,800 Hz and high 1,800 to 10,000 Hz frequency bands, compared to the bearing noise in the low frequency band at 50 to 300 Hz. The lubricant noise is superimposed by the noise peaks that occur when hard particles roll over the rolling elements in the form of shock pulses on the bearing ring. The evaluation of the noise behavior is based on the SKF BeQuiet ⁺ method.

• GNX: slightly worse than GN1 (very poor noise behavior)
• GN1: > 95% of all peaks are <= 40 µm / s (poor noise behavior)
• GN2: > 95% of all peaks are <= 20 µm / s; > 98% of all peaks are <= 40 µm / s (average noise behavior)
• GN3: > 95% of all peaks are <= 10 µm / s; > 98% of all peaks are <= 20 µm / s; > 100% of all peaks are <= 40 µm / s (good noise behavior)
• GN4: > 95% of all peaks are <= 5 µm / s; > 98% of all peaks are <= 10 µm / s; > 100% of all peaks are <= 20 µm / s (very good noise behavior)

The better the noise behavior of a lubricating grease, the lower the vibrations of the bearing caused by the lubricant. This is synonymous with a low load on the bearing and leads to a longer functional life of the bearing.

The object of the present invention is to provide a high-temperature oil and high-temperature grease which meets the above-mentioned requirements. In particular, the lubricating oil or grease should show a good lubricating effect at high temperature over a long period of time. Furthermore, the cracking residues formed should not be laked up, but should be able to be dissolved again by fresh fat. Furthermore, the high-temperature lubricant should have good hydrolytic stability, be corrosion- and wear-resistant, as well as good oxidation resistance and good low-temperature behavior adapted to the requirements. This is defined for lubricating oils by the pour point and for lubricating greases by the flow pressure at low temperatures. In addition, the high-temperature grease should exhibit good noise behavior, have long running times and essentially cause no signs of wear on the devices.

1. a) 93,9 bis 45 Gew.-% mindestens eines Öls, ausgewählt aus der Gruppe Estolide
2. b) 6 bis 45 Gew.-% eines Polymers, nämlich eines vollhydrierten Polyisobutylen oder einer Mischung aus hydrierten und vollhydrierten Polyisobutylen;
3. c) 0,1 bis 10 Gew.-% Additive einzeln oder in Kombination, ausgewählt aus der Gruppe bestehend aus Korrosionsschutzadditiven, Antioxidantien, Verschleißschutzadditiven, UV-Stabilisatoren, anorganischen oder organischen Feststoffschmierstoffen.

According to the invention, this object is achieved by a high-temperature oil comprising the following components:

1. a) 93.9 to 45% by weight of at least one oil selected from the group Estolide
2. b) 6 to 45% by weight of a polymer, namely a fully hydrogenated polyisobutylene or a mixture of hydrogenated and fully hydrogenated polyisobutylene;
3. c) 0.1 to 10% by weight of additives, individually or in combination, selected from the group consisting of anti-corrosion additives, antioxidants, anti-wear additives, UV stabilizers, inorganic or organic solid lubricants.

1. a) 91,9 bis 25 Gew.-% mindestens eines Öls, ausgewählt aus der Gruppe Estolide,
2. b) 6 bis 45 Gew.% eines Polymers, nämlich eines hydrierten oder vollhydrierten Polyisobutylen oder einer Mischung aus hydrierten oder vollhydrierten Polyisobutylen;
3. c) 0,1 bis 10 Gew.-% Additive einzeln oder in Kombination, ausgewählt aus der Gruppe bestehend aus Korrosionsschutzadditiven, Antioxidantien, Verschleißschutzadditiven, UV-Stabilisatoren, anorganischen oder organischen Feststoffschmierstoffen und
4. d) 2 bis 20 Gew.-% Verdickungsmittel.

According to the invention, this object is achieved by a high-temperature grease comprising the following components:

1. a) 91.9 to 25% by weight of at least one oil selected from the group Estolide,
2. b) 6 to 45% by weight of a polymer, namely a hydrogenated or fully hydrogenated polyisobutylene or a mixture of hydrogenated or fully hydrogenated polyisobutylene;
3. c) 0.1 to 10% by weight of additives, individually or in combination, selected from the group consisting of corrosion protection additives, antioxidants, wear protection additives, UV stabilizers, inorganic or organic solid lubricants and
4. d) 2 to 20% by weight of thickener.

It has surprisingly been found that the high-temperature oil according to the invention and the high-temperature grease according to the invention are distinguished by excellent performance. The high-temperature oil or high-temperature grease according to the invention thus exhibits high thermal stability combined with a long service life and good lubricating properties.

The high-temperature oil according to the invention comprises an estolide or a mixture of different estolides as the ester compound.

The preferred viscosities of the estolides, measured at 40 ° C., are between 30 and 500 mm ² / sec. Viscosities of 30 to 140 mm ² / sec are particularly preferred.

Estolides are understood as meaning ester compounds which are prepared with acid or enzymatic catalysis from fatty acids, preferably oleic acid or dicarboxylic acids, or a mixture of both. The acid function attacks the double bond of a neighboring oil fatty acid molecule, so that a higher molecular ester compound is formed. The terminal acid group is then usually esterified with an alcohol, preferably 2-ethylhexanol, and then the remaining double bonds are hydrogenated or esterified with carboxylic acid, e.g. acetic acid. Other alcohols such as isoamyl alcohol or Guebert alcohols are also conceivable for the esterification of the terminal acid group.

Further estolides can also be synthesized via a condensation of hydroxycarboxylic acids or a condensation of hydroxycarboxylic acids with fatty acids, for example oleic acid or stearic acid derivatives. The chain length of the hydroxycarboxylic acids or unsaturated acids used can range from C ₆ to C ₅₄ . The acids can contain further functional groups, for example amines, ethers, sulfur-containing groups.

In addition, esterification with alpha-olefins or beta-farneses is also conceivable.

The high temperature oil according to the invention can contain a second oil which comprises an alkyl aromatic. An aromatic is preferably used. According to the invention, an aromatic is understood to mean a monocyclic, bicyclic or tricyclic ring system with four to fifteen carbon atoms, the monocyclic ring system being aromatic or at least one of the rings in a bicyclic or tricyclic ring system being aromatic. A bicyclic ring system, which preferably has 10 carbon atoms, is preferably used.

The aromatic is preferably substituted by one or more aliphatic substituents. The aromatic with one to four aliphatic substituents and in particular with two or three aliphatic substituents is particularly preferred substituted.

According to the invention, an alkyl group is a saturated aliphatic hydrocarbon group having 1 to 30, preferably 3 to 20, more preferably 4 to 17 and in particular 6 to 15 carbon atoms. An alkyl group can be linear or branched and is optionally substituted with one or more of the above-mentioned substituents.

According to the invention, the lubricating oil particularly preferably contains at least one aliphatically substituted naphthalene, in particular at least one alkyl-substituted naphthalene. The naphthalene is preferably substituted with one to four aliphatic substituents and in particular with two or three aliphatic substituents.

Practical tests have shown that mixtures of differently substituted naphthalenes, that is to say mixtures of naphthalenes which have different degrees of substitution and different aliphatic substituents, are particularly suitable. In this case, by varying the composition of the mixture, the properties, such as the viscosity, of the high-temperature lubricant can be set particularly easily. Aliphatically substituted naphthalenes are also distinguished by excellent solution properties and high thermo-oxidative stability.

The viscosity, measured at 40 ° C., of the aliphatic substituted naphthalene is preferably from 30 to 600 mm ² / s, more preferably from 30 to 300 m ² / s.

The high-temperature oil according to the invention also comprises a fully hydrogenated polyisobutylene.

A suitable choice of polyisobutylene, in particular with regard to the degree of hydrogenation and molecular weight, can influence the properties of the oil according to the invention, for example its kinematic viscosity and, above all, its residue formation, in the desired manner. The polyisobutylene
is used in fully hydrogenated form; a mixture of hydrogenated and fully hydrogenated polyisobutylene can also be used. That Polyisobutylene is present in the composition in an amount of 6 to 45% by weight, 10 to 45% by weight, in particular 15 to 45% by weight, are preferably used.

The high-temperature oil according to the invention also comprises from 0.1 to 10% by weight, additives, which are used individually or in combination and are selected from the group consisting of corrosion protection additives, antioxidants, wear protection additives, UV stabilizers, inorganic or organic solid lubricants.

The high-temperature grease according to the invention comprises 91.9 to 25% by weight of an oil from the group of the estolides.

The high temperature grease according to the invention can contain a second oil which comprises an alkyl aromatic. An aromatic is preferably used. According to the invention, an aromatic is understood to mean a monocyclic, bicyclic or tricyclic ring system with four to fifteen carbon atoms, the monocyclic ring system being aromatic or at least one of the rings in a bicyclic or tricyclic ring system being aromatic. A bicyclic ring system, which preferably has 10 carbon atoms, is preferably used.

The aromatic is preferably substituted by one or more aliphatic substituents. The aromatic is particularly preferably substituted with one to four aliphatic substituents and in particular with two or three aliphatic substituents.

According to the invention, an alkyl group is a saturated aliphatic hydrocarbon group having 1 to 30, preferably 3 to 20, more preferably 4 up to 17 and in particular 6 to 15 carbon atoms. An alkyl group can be linear or branched and is optionally substituted with one or more of the above-mentioned substituents.

According to the invention, the lubricating grease particularly preferably contains at least one aliphatically substituted naphthalene, in particular at least one alkyl-substituted naphthalene. The naphthalene is preferably substituted with one to four aliphatic substituents and in particular with two or three aliphatic substituents.

Practical tests have shown that mixtures of differently substituted naphthalenes, that is to say mixtures of naphthalenes which have a different degree of substitution and different aliphatic substituents, are particularly suitable. In this case, by varying the composition of the mixture, the properties, such as the viscosity, of the high-temperature lubricant can be set particularly easily. Aliphatically substituted naphthalenes are also distinguished by excellent solution properties and high thermo-oxidative stability.

The viscosity, measured at 40 ° C., of the aliphatic substituted naphthalene is preferably from 30 to 600 mm ² / s, more preferably from 30 to 300 m ² / s.

The high-temperature grease according to the invention contains at least one oil from the group of estolides.

Preferred viscosities, measured at 40 ° C., are between 30 and 500 mm ² / sec. Viscosities of 30 to 140 mm ² / sec are particularly preferred.

The high-temperature grease according to the invention also comprises a fully hydrogenated one

Polyisobutylene. A suitable choice of polyisobutylene, in particular with regard to the degree of hydrogenation and molecular weight, can influence the properties of the fat according to the invention, for example its kinematic viscosity, in the desired manner. The polyisobutylene is in fully hydrogenated

A mixture of hydrogenated and fully hydrogenated polyisobutylene can also be used. Fully hydrogenated polyisobutylenes are preferably used. The polyisobutylene is in an amount of 6 to 45% by weight are present in the composition, preferably 10 to 45% by weight, in particular 15 to 45% by weight, are used.

According to a further preferred embodiment, the polyisobutylene has a number average molecular weight of 115 to 10,000 g / mol, preferably 160 to 5000 g / mol.

The high-temperature grease according to the invention also comprises from 0.1 to 10% by weight, additives, which are used individually or in combination and are selected from the group consisting of corrosion protection additives, antioxidants, wear protection additives, UV stabilizers, inorganic or organic solid lubricants.

The high-temperature grease according to the invention also comprises a thickening agent. The thickener in the high-temperature grease of the lubricant composition according to the invention is either a reaction product of a diisocyanate, preferably 2,4-diisocyanatotoluene, 2,6-diisocyanatotoluene, 4,4'-diisocyanatodiphenylmethane, 2,4'-diisocyanatophenylmethane, 4,4'-diisocyanatodi- phenyl, 4,4'-diisocyanato-3-3'-dimethylphenyl, 4,4'-diisocyanato-3,3'-dimethylphenylmethane, which can be used individually or in combination, with an amine of the general formula R ' ₂ -NR , or a diamine of the general formula R ' ₂ -NR-NR' ₂ , where R is an aryl, alkyl or alkylene radical having 2 to 22 carbon atoms and R ', identically or differently, is a hydrogen, an alkyl, alkylene or aryl radical is, or with mixtures of amines and diamines
or
is selected from Al complex soaps, metal single soaps of the elements of the first and second main group of the periodic table, metal complex soaps of the elements of the first and second main group of the periodic table, bentonites, sulfonates, silicates, Aerosil, polyimides or PTFE or a mixture of the above Thickener.

As additives for high-temperature oils and greases, the following additives have particularly good physical and chemical properties:
The addition of antioxidants can reduce or even prevent the oxidation of the oil or fat according to the invention, especially when it is used. In the event of oxidation, undesirable free radicals can arise and, as a result, more decomposition reactions of the high-temperature lubricant occur. The high temperature fat is stabilized by adding antioxidants.

Antioxidants particularly suitable according to the invention are the following compounds:
Styrenated diphenylamines, diaromatic amines, phenolic resins, thiophenolic resins, phosphites, butylated hydroxytoluene, butylated hydroxyanisole, phenyl-alphanaphthylamine, phenyl-beta-naphthylamine, octylated / butylated diphenylamine, dialpha-tocopherol, phenyl-phenyl-phenol, sulfur-propane, phenyl-tert-butyl-phenyl compounds , Phenolic compounds and mixtures of these components.

The high-temperature grease can also contain corrosion protection additives, metal deactivators or ion complexing agents. These include triazoles, imidazolines, N-methylglycine (sarcosine), benzotriazole derivatives, N, N-bis (2-ethylhexyl) -ar-methyl-1H-benzotriazole-1-methanamine; n-Methyl-N (1-oxo-9-octadecenyl) glycine, mixture of phosphoric acid and mono- and diisooctyl esters reacted with (C _11-14 ) -alkylamines, mixture of phosphoric acid and mono- and diisooctyl esters reacted with tert-alkylamine and primary (C _12-14 ) amines, dodecanoic acid, triphenyl phosphorothionate and amine phosphates. Commercially available additives are the following: IRGAMET® 39, IRGACOR® DSS G, amine O; SARKOSYL® O (Ciba), COBRATEC® 122, CUVAN® 303, VANLUBE® 9123, CI-426, CI-426EP, CI-429 and CI-498.

Further anti-wear additives are amines, amine phosphates, phosphates, thiophosphates, phosphorothionates and mixtures of these components. The commercially available anti-wear additives include IRGALUBE® TPPT, IRGALUBE® 232, IRGALUBE® 349, IRGALUBE® 211 and ADDITIN® RC3760 Liq 3960, FIRC-SHUN® FG 1505 and FG 1506, NA-LUBE® KR-015FG, LUBEBOND .®, FLUORBOND ® FG, SYNALOX® 40-D, ACHESON® FGA 1820 and ACHESON® FGA 1810.

Furthermore, the grease can contain solid lubricants such as PTFE, BN, pyrophosphate, Zn oxide, Mg oxide, pyrophosphates, thiosulfates, Mg carbonate, Ca carbonate, Ca stearate, Zn sulfide, Mo sulfide, W sulfide, Sn -Sulfide, graphite, graphene, _{nanotubes, SiO 2} modifications or a mixture thereof.

Practical tests have shown that the high-temperature oil or fat according to the invention shows no or negligible decomposition phenomena up to a temperature of 250 ° C. This means that less than 10% of the lubricant decomposes.

The high-temperature oil or fat according to the invention can be used as a further base oil, preferably selected from the group consisting of mineral oil, aliphatic carboxylic acid and dicarboxylic acid esters, fatty acid triglycerides, pyromellitic acid esters, diphenyl ethers, phloroglucinic esters and / or poly-alpha-olefins, alpha-olefins Contain copolymers.

• enthält
• ein Estolid, wobei vorzugsweise die Hauptbestandteile des Estolides gewonnen werden durch chemische oder enzymatische Prozesse ausgehend von nativen Ölen aus der Gruppe Sonnenblumenöl, Rapsöl, Rizinusöl, Leinöl, Maisöl, Diestelöl, Sojabohnenöl, Leinsamenöl, Erdnussöl, "Lesqueralle"-Öl, Palmöl, Olivenöl oder Mischungen aus den vorgenannten Ölen.

The high temperature oil or fat according to the invention

• contains
• an estolide, whereby the main components of the estolide are preferably obtained by chemical or enzymatic processes starting from native oils from the group of sunflower oil, rapeseed oil, castor oil, linseed oil, corn oil, diestel oil, soybean oil, linseed oil, peanut oil, "Lesqueralle" oil, palm oil, olive oil or mixtures of the aforementioned oils.

Practical tests have shown that the high-temperature oil or grease according to the invention, due to its physical and chemical properties, is excellent for use in chains, roller and plain bearings, in vehicle technology, conveyor technology, mechanical engineering, office technology and in industrial systems and machines, but also in the areas of household machines and entertainment electronics. Due to its good temperature resistance, it can also be used at high operating temperatures of up to 260 ° C, preferably at temperatures of 150 to 250 ° C.

The invention also relates to a method of making that described above High temperature oil or grease in which the base oils and the additives are mixed with one another.

The invention will now be explained in more detail with the aid of the following examples.

Examples 1 to 2 Production of a high temperature oil according to the invention

Estolides or aliphatically substituted naphthalenes are placed in a stirred tank. At 100 ° C., the polyisobutylene and, if necessary, a further oil are added with stirring. Then the mixture is stirred for 1 hour to obtain a homogeneous mixture. The anti-wear agents and the antioxidant are added to the kettle at 60 ° C. while stirring. After approx. 1 hour, the finished oil can be filled into the containers provided.

Composition of high temperature oils:

Table 1 example 1 Comparative example 1 Trimellitate 0.0 63.0 Estolide 1 44.0 0.0 Estolide 2 19.0 0.0 hydrogenated PIB 30.4 30.4 amine antioxidant 2.0 2.0 phenolic antioxidant 1.0 1.0 Wear protection EP / WA 3.5 3.5 Corrosion protection 0.1 0.1 Solubility of the residues very good (4) very good (4) Table 2 Example 2 Comparative example 2 Trimellitate 1 0 76.0 alkylated naphthalene 76.0 0.0 hydrogenated PIB 20.0 20.0 amine antioxidant 4.0 4.0 Solubility of the residues very good (4) very good (4)

Example 2 is not according to the invention.

The basic data of the oil examples can be found in Table 3. <u> Table 3 </u> Recipe example 1 Comparative example 1 Example 2 Comparative example 2 Eisenmann test [250 ° C, 72h] Solvability 4th 4th 4th 4th Basic data Flash point (° C) > 250 > 250 > 250 > 250 kin. V40 280.0 270.0 300.0 140.5 kin. V100 29.00 25.0 25.00 16.13 VI 137 120.0 105 121

Furthermore, the friction behavior of the oils in the SRV was measured based on DIN 51834-2 and the evaporation loss in the dynamic TGA. The results are shown in Tables 4 and 5 and are graphed in FIG Figures 1 and 2 reproduced. <u> Table 4 </u> example 1 Comparative example 1 Example 2 Comparative example 2 SRV TST (250 N) 50 - 120 ° C 0.116 0.112 0.156 0.091 120-140 ° C 0.111 0.127 0.155 0.091 140-160 ° C 0.105 0.141 0.158 0.128 160-180 ° C 0.1 0.145 0.163 0.139 180-200 ° C 0.095 0.143 0.171 0.165 200-210 ° C 0.08 0.137 0.177 0.194 210-220 ° C 0.086 0.132 0.175 0.206 220-230 ° C 0.085 0.129 0.179 0.208 230-240 ° C 0.087 0.126 0.185 0.208 240-250 ° C 0.091 0.121 0.189 0.206 250 ° C isothermal 0.093 0.118 0.186 0,201 example 1 Comparative example 1 Example 2 Comparative example 2 TGA dynamic 120 ° C 0.1 0.1 0.1 0.1 140 ° C 0.3 0.2 0.3 0.2 160 ° C 0.6 0.5 0.4 0.4 180 ° C 1 0.9 0.9 0.7 200 ° C 1.7 1.4 1.8 1.2 220 ° C 2.8 2.3 3.6 2.2 240 ° C 4.6 3.7 6.6 3.7 260 ° C 7.7 5.9 11.7 6.3

Examples 3 to 8 Production of a high temperature grease according to the invention

The base oil is placed in a stirred tank. At 100 ° C., the polyisobutylene and, if necessary, a further oil and the thickener are added with stirring. The thickener results from an in situ reaction of the reactants used in the base oil. The mixture is then heated to 150 ° C. to 210 ° C., stirred for several hours and cooled again. In the cooling process at approx. 60 ° C, the necessary wear protection agents, antioxidants and corrosion protection agents are added. A homogeneous mixture of the fat is obtained by the final homogenization step using a roller, colloid mill or the Gaulin.

The compositions of the high temperature greases are shown in Table 6. <u> Table 6 </u> Type Li complex Li complex Li complex Di-urea Di-urea Di-urea Example 3 Example 4 Example 5 Example 6 Example 7 Example 8 Trimellitic acid ester [% by weight] 60 0 0 65.2 0 0 Estolide [wt.%] 0 0 56 0 0 65.2 alkylated naphthalene [wt.%] 0 64 0 0 65.2 0 fully hydrogenated polyisobutylene [% by weight] 26th 25th 25th 25th 25th 25th Additive package [wt.%] 4th 1 4th 1 1 1 Thickener concentration [wt.%] 10 10 15.0 8.8 8.8 8.8

• Beispiel 3: LiOH, 12-Hydroxystearinsäure, Azelainsäure,
• Beispiel 4: LiOH, 12-Hydroxystearinsäure, Azelainsäure,
• Beispiel 5: LiOH, 12-Hydroxystearinsäure, Azelainsäure,
• Beispiel 6: Di-Harnstoff; Methylen-Di-phenyl-diisocyanat (MDI), Octylamin, Oleylamin
• Beispiel 7: Di-Harnstoff; MDI, Octylamin, Oleylamin
• Beispiel 8: Di-Harnstoff; MDI, Octylamin, Oleylamin

Examples 4 and 7 are not according to the invention) The thickeners used in Examples 3 to 8 are:

• Example 3: LiOH, 12-hydroxystearic acid, azelaic acid,
• Example 4: LiOH, 12-hydroxystearic acid, azelaic acid,
• Example 5: LiOH, 12-hydroxystearic acid, azelaic acid,
• Example 6: Di-urea; Methylene-diphenyl-diisocyanate (MDI), octylamine, oleylamine
• Example 7: di-urea; MDI, octylamine, oleylamine
• Example 8: di-urea; MDI, octylamine, oleylamine

The general characteristics of the fat samples 3 to 8 are shown in Table 7. <u> Table 7 </u> Characteristics Example 3 Example 4 Example 5 Example 6 Example 7 Example 8 Walk penetration according to 60 DT [DIN ISO 2137] 284 283 278 232 232 300 Walk penetration according to 100000 DT [DIN ISO 21371 324 319 319 254 254 338 Drop point [C °] [DIN ISO 2176 > 300 > 300 > 300 > 300 280 292 Flow pressure -20 ° C; [mbar] [DIN 51805] > 2000 275 284 575 525 <1400 Flow pressure -30 ° C; [mbar] [DIN 51805] > 2000 425 675 <1400 <1400 <1400 Oil cut-off 40 ° C / 168h; 51817] 3.80 3 1.70 1.2 0.10 5.60 Oil cut-off 150 ° C / 30h; [% By weight] [FTMS 761 C] 7.4 7.5 2.50 0.20 0.30 5.00 Evaporation loss 150 ° C / 24 ° C [DIN 58397 part 1] 2 5.3 2.50 1.6 3.5 2.1 Static water resistance [DIN 51807] 1 2 1.00 0 1 1

The evaporation losses of the various fat samples at 150 ° C after 30 hours are between 2% and 5%, which underlines the very good thermal stability of these fat concepts.

Oil separation has a decisive influence on the lubricating effect of a grease. It must be ensured that, on the one hand, the oil separation is not too high and the oil runs out of the bearing and is therefore no longer available to the tribo-system and, on the other hand, no oil separation can be observed and the lubricating effect of the grease is lost. The oil separation should ideally be between 0.5 and 8% by weight so that an optimal lubricating film can form in the bearing.

The greases in the examples were subjected to an FE 9 roller bearing test according to DIN 51 821, in which the service life of the greases examined is determined and the upper service temperature of lubricating greases in roller bearings at medium speeds and medium axial loads is determined.

The examined fats and the results of the L10 and L50 values are in Table 8 The fats tested and the results of the L10 and L50 values are shown in Table 8. <u> Table 8 </u> Example 3 Example 4 Example 5 Example 6 Example 7 Example 8 FE 9 [180 ° C, 6000 rpm, 1500N] L 50 (h) 249 > 100 207 146 > 100 > 100 L 10 (h) 169 > 50 138 72 > 50 > 50

Table 8 shows that the running times due to the use of PIB in conjunction with various base oils have long running times and are therefore suitable for high application temperatures in continuous operation.

In addition, the noise behavior after the SKF Be Quiet ⁺ fats according to Examples 3 to 8 was measured. The results are given in Table 9. <u> Table 9 </u> Example 3 Example 4 Example 5 Example 6 Example 7 Example 8 Noise test [BeQuiet + SKF] GN4 GN3 GN3 GN2 GN3 GN4

The use of fully hydrogenated polyisobutylene has a very positive effect on the noise behavior of the various fat formulations. With the exception of Example 6, good to very good noise properties can be achieved.

The properties of the fat according to Example 3, in which fully hydrogenated PIB was used, was now compared with a fat (comparative example 3) that contained a PIB in which double bonds were still present, that is to say a not fully hydrogenated PIB.

The other composition of the fat according to comparative example 3 corresponded to that of example 3. Example 3 Comparative example 3 FE 9 [180 ° C, 6000 rpm, 1500N]. L 50 (h) 249 126 L 10 (h) 169 72 Noise test [BeQuiet + SKF] GN4 GN1 Loss of evaporation [DIN ISO 58397] 170 ° C / 24h 4.3 5.1 Evaporation loss [DIN ISO 58397] 180 ° C / 24h 6.9 7.4 Walk penetration according to 60 DT [DIN ISO 2137] 284 301 Milled penetration according to 100000 DT [DIN ISO 2137] 324 356 Corrosion effect of lubricants on copper [DIN ISO 51811] 150 ° C / 24h 1a n / A Oil cut-off 150 ° C / 30h; [% By weight] [ASTM D 6184 7.4 8.4 Oil cut-off 150 ° C / 40h; [% By weight] [ASTM D 6184 17.9 14.7 Oil cut-off 168 ° C / 40h; [% By weight] [DIN 51817] 3.8 6.5 Testing of fat greases for corrosion-preventing properties [DIN 51801 / ISO 11007 0 n / A Drop point [C °] [DIN ISO 2176] > 300 295.0 Evaporation loss 150 ° C / 24 ° C [DIN 58397 part 1] 2 2.4 Static water resistance [DIN 51807] 90 ° C 0 n / A

The comparison of the fats with fully hydrogenated PIB and not fully hydrogenated PIB in Table 10 shows that the fat of Example 3 shows a doubled running time in the FE9 test, has lower evaporation losses and a significantly better noise behavior.

To demonstrate the advantageous properties of the oil that contains fully hydrogenated PIB, this was compared with an oil that contains a partially hydrogenated PIB. Table 11 shows the results.

Table 11

Table 11 template Oil 1 Oil 2 Estolide 1 32.966 wt% 32.966 wt% Estolide 2 26.874 wt% 26.874 wt% fully hydrogenated PIB 33.65% by weight ----- part hydrietes PIB ----- 33.65% by weight Antioxidant 3% by weight 3% by weight AW 3.5 wt% 3.5 wt% Corrosion protection 0.01 wt% 0.01 wt% Test methods V40 (mm ² / s) 277.8 277.6 V100 (mm ² / s) 28.28 27.90 Viscosity index 136 134 Eisenmann test 72h / 250 ° C residue (%) 6.6 8.0 Eisenmann test 72h / 250 ° C solvability 4th 1 Eisenmann test 120h / 220 ° C residue (%) 13.8 19.2 Eisenmann test 120h / 220 ° C solvability 3 1 HTG chain test bench 220 ° C / 2600N / 2 _{m / s} (h) 15th 13th 4 = residue can be dissolved very well after complete evaporation
3 = residue easily dissolvable after complete evaporation
2 = residue partially dissolvable after complete evaporation
1 = residue cannot be dissolved after complete evaporation

Table 11 shows that there are significant differences when using fully hydrogenated and partially hydrogenated PIB. For example, it is no longer possible to partially dissolve the residue on the basis of the partially hydrogenated PIV, while the oil with the fully hydrogenated PIB has very good redissolving properties.

Claims (6)

1. A high-temperature oil, comprising:

   a) 93.9 to 45 wt.-% of at least one oil from the group of estolides;

   b) 6 to 45 wt.-% of a polymer, specifically a fully hydrogenated polyisobutylene or a mixture of hydrogenated and fully hydrogenated polyisobutylene;

   c) 0.1 to 10 wt.-% of additives, individually or in combination, selected from the group consisting of anticorrosion additives, antioxidants, antiwear additives, UV stabilisers, inorganic or organic solid lubricants.
2. The high-temperature oil according to claim 1, in which the oil component comprises as a further oil a compound selected from the group consisting of mineral oil, aliphatic carboxylic and dicarboxylic esters, fatty acid triglycerides, pyromellitic esters, diphenyl ethers, phloroglucinol esters and/or poly-alpha-olefins, alpha-olefin copolymers.
3. A high-temperature grease, comprising:

   a) 91.9 to 25 wt.-% of at least one oil from the group of estolides;

   b) 6 to 45 wt.-.% of a polymer, selected from the group consisting of a fully hydrogenated polyisobutylene or a mixture of hydrogenated and fully hydrogenated polyisobutylene;

   c) 0.1 to 10 wt.-% of additives, individually or in combination, selected from the group consisting of anticorrosion additives, antioxidants, antiwear additives, UV stabilisers, inorganic or organic solid lubricants, and

   d) 2 to 20 wt.-% of thickener.
4. The high-temperature grease according to claim 3, in which the oil component comprises as a further oil a compound selected from the group consisting of mineral oil, aliphatic carboxylic and dicarboxylic esters, fatty acid triglycerides, pyromellitic esters, diphenyl ethers, phloroglucinol esters and/or poly-alpha-olefins, alpha-olefin copolymers.
5. The high-temperature grease according to claim 3, in which the thickener is selected from the group consisting of urea, Al complex soaps, simple metal soaps of the elements of the first and second main groups of the Periodic Table, metal complex soaps of the elements of the first and second main groups of the Periodic Table, bentonites, sulfonates, silicates, Aerosil, polyimides, PTFE or a mixture of the aforementioned thickeners.
6. A use of the high-temperature oil or high-temperature grease according to one of the preceding claims for the lubrication of roller bearings and plain bearings, in vehicle technology, in conveying technology, in mechanical engineering, in office technology, and in industrial plants and machines, but also in the areas of household appliances, of consumer electronics and for the lubrication of chains, chain rollers, and belts of continuous presses.

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