WO2019016412A1

WO2019016412A1 - Lubricant composition

Info

Publication number: WO2019016412A1
Application number: PCT/EP2018/069953
Authority: WO
Inventors: Axel Figge; Lutz KOGEL; Tobias ASAM; Patrick DEGEN; Christopher FOLLAND
Original assignee: Carl Bechem Gmbh
Priority date: 2017-07-21
Filing date: 2018-07-23
Publication date: 2019-01-24
Also published as: CN111315853A; EP3431574A1

Abstract

The invention relates to a lubricant composition, more particularly a lubricating grease composition, based on an aqueous base oil, containing a thickener component made of one or more thickeners or salts thereof, and containing a polymer component made of one or more natural or chemically modified polymers or salts thereof. The thickener can be obtained by combining a mono- or dicarboxylic acid or mixtures thereof and alkanolamines, alkylamines or mixtures thereof.

Description

S e c tio n to m e n t i o n s

The invention relates to a base oil for a lubricant composition, in particular a lubricating grease composition and to processes for the preparation of this lubricant composition.

Greases typically consist of 65 to 95% of a base oil, 3 to 30% of a thickener component, and 0 to 10% of additives (Wilfried J. Bartz: Greases, Composition, Properties, Testing and Use, Expert 2000, p. The base oils usually consist of natural or synthetic oils. Such grease compositions are for example from

WO08154997 A1 is known.

Surprisingly, it has now been found that the base oil for the preparation of a lubricant composition can be aqueous. Preferably, it is watery and oil-free. In the simplest case, the base oil may consist of water.

Preferably, the base oil contains one or more polymers or salts thereof (polymer component). By the polymer component and / or the proportions of water to polymer components, the chemical and / or physical properties of the base oil, in particular the viscosity can be influenced.

By using the base oil of the invention for the preparation of a lubricant composition, lubricant compositions having advantageous electrical conductivities can be formed. Preferably, the conductivities of the lubricants according to the invention are in the range of 10 ^"12 and ^10" ³ S / cm, preferably in the range of 10 ^"9 and ^{10" 3} S / cm, particularly preferably in the Range between 10 ^"7 and 10 ^{" 3} , in particular in the range between 10 ^"5 and 10 ^{" 3} S / cm. This opens up the possibility of using the lubricant compositions according to the invention, in particular the fats according to the invention, as "current bridges", for example in roller bearings in electrical machines ,

Furthermore, the aqueous base oils according to the invention make it possible to reduce the oil content in the lubricant composition, advantageously dispensing with oils entirely. In a particularly preferred embodiment, the base oils according to the invention and the lubricant compositions produced therewith are oil-free, in particular mineral oil-free. Thus, the base oils and lubricant compositions according to the invention can preferably be used in devices in which possible leaks would directly lead to contamination of the environment. This is particularly important in applications where contamination of surface water is to be feared. A particularly preferred field of application is therefore the use of the lubricant compositions of the invention in underwater applications, such as in underwater turbines.

The invention therefore relates to a lubricant composition, preferably a lubricating grease composition, comprising water and a first component of one or more thickeners or salts thereof (thickener component), the relative proportion of water being not more than 70% by weight, preferably not more than 50% by weight. , particularly preferably not more than 40% by weight, very particularly preferably not more than 35% by weight, if the thickener component has a dropping point of not more than 260 ° C., preferably of not more than 280 ° C., particularly preferably of 300 ° C.

The relative proportion of water, however, is at most 40 wt .-%, preferably at most 35 wt .-%, when the thickener component has a melting point of more than 260 ° C, preferably more than 280 ° C, more preferably more than 300 ° C. These thickeners are typically solids. These are added to the base oil to make the grease composition Added solid. A lubricant composition produced in this way can be pasty. The resulting lubricant composition is then a paste, ie a solid state dispersion in a liquid. The invention also provides the use of the aqueous base oil for producing a lubricating grease composition and a process for producing a

A lubricant composition comprising the following steps:

(i) providing an aqueous base oil, preferably a mixture containing water, and one or more water-soluble polymers or salts thereof (polymer component);

(iia) contacting the base oil with the thickener component

(iii) optionally heating the mixture

(iv) optionally adding additives

In this case, bringing the thickener with the base oil by adding the thickener or by an in-situ production of the thickener in the base oil done.

For the purposes of the invention, the "base oil" refers to a carrier medium, in particular a dispersing agent, which is suitable for absorbing, in particular dispersing, the thickener component and any additives present Properties significantly affect the lubrication properties of the resulting lubricant composition, in particular grease composition In a preferred embodiment, the base oil contains a

Polymer component.

"Grease compositions" are semi-liquid to consistent dispersions of a thickener component in a liquid carrier medium, especially a base oil. "Grease compositions can resist external, shape-changing forces." Grease compositions have a yield point. Preferably, the molecules in grease compositions have a higher state of order compared to the molecules in liquid lubricant compositions. A "thickener" is a substance that has the ability to form a three-dimensional network in a medium, which may preferably consist of fibrous structural units (fibrils), which may in particular consist of crystallites and micelles, which may be linked by association as molecular aggregates The molecules of the base oil are preferably embedded in this three-dimensional network through molecular interactions, capillary forces, and mechanical inclusions, thickeners may also be present as salts, unless otherwise stated, the term "thickener" always covers the salts thereof.

The use of a thickener in the base oil preferably results in the grease composition having a defined yield point. The reason for this is the above-described three-dimensional network formed by the thickener molecules as a result of physical interactions, as a result of which, in part, the molecules of the base oil can be bound or incorporated into the three-dimensional matrix.

The "melting point" refers to the temperature at which the liquid and solid phases of a substance are in equilibrium at normal pressure (1013 hPa) At the melting point, the substance changes from the solid to the liquid state, preferably without any chemical change.

The "dropping point" refers to the meltability of solid fats, in particular lubricants The dropping point in the sense of the invention is the temperature at which the lubricant drips under test weight under test conditions of, for example, standard IP 396, in particular begins to flow.

The term "polymer component" is understood to mean one or more water-soluble polymers or salts thereof, unless otherwise stated, the term "polymer" always includes salts of the polymer. "By combining the polymer component with water, a thickened liquid having an increased viscosity can be compared In addition, the polymer, in particular the polymer component, can also have lubricating properties. Advantageous embodiments of the invention will be explained in detail below.

In a preferred embodiment of the grease composition of the invention, the relative amount of water is at least 10

% By weight, preferably at least 15% by weight, particularly preferably at least 20% by weight, very particularly preferably at least 30% by weight, if the thickener component has a dropping point of not more than 260 ° C., preferably not more than 280 ° C., particularly preferably of 300 ° C.

Alternatively, the relative amount of water in this embodiment is at least 10 wt%, preferably at least 15 wt%, more preferably at least 20 wt%, most preferably at least 30 wt% when the thickener component is a melting point of not more than 260 ° C, preferably of not more than 280 ° C, particularly preferably of 300 ° C.

As already stated, it is particularly advantageous if the base oil contains a polymer component. Preferably, the relative proportion of the polymer component in the base oil is 0.05 to 15 wt%, preferably 0.1 to

10 wt .-%, in particular at 0.1 to 5 wt .-%. This is especially true when the polymer component is a cellulose ether or salt thereof, especially the sodium salt of carboxymethylcellulose. It has also been found that Schmiefettzusammensetzungen can be obtained with particularly positive properties when the weight ratio of the polymer component to the thickener component in the grease composition between 1:60 and 1: 1, preferably between 1: 40 and 1: 3, in particular between 1: 30 and 1: 5.

Besides the resulting advantages by adjusting the proportions by weight of the polymer component, it is also advantageous if the relative proportion of the thickener component to the total composition is at least 20% by weight, preferably at least 30%, more preferably at least 35% by weight preferably more than 35 wt .-% is. Particularly preferred lubricant grease compositions according to the invention result in a relative proportion of the water between 25 and 95 wt .-%, a proportion of the polymer component between 0.5 and 4 wt .-% and a proportion between 10 and 70 wt .-% of the thickener component.

Preferably, the base oil and the lubricating grease composition prepared using the base oil comprises water-soluble polymers or salts thereof (polymer component) selected from the group consisting of: a) natural polymers such as polysaccharides, inorganic polysaccharides, natural rubbers and lignins;

b) chemically modified polymers such as cellulose ethers and modified starches;

c) synthetic polymers such as polyvinyl alcohols, polyethylene glycols, polyvinylpyrrolidones or mixtures thereof.

The term "natural polymer" (also referred to as "biopolymer") refers to polymers whose origin is of biological origin and which contain no chemical modifications.

By a "semi-synthetic polymer" is meant a chemically-modified natural polymer, examples being carboxyalkyl cellulose (such as carboxymethyl cellulose), hydroxyalkyl cellulose (such as hydroxypropyl cellulose) or cellulose acetate.

"Synthetic polymers" refers to polymers obtained from chemical synthesis / polymerization, examples being polyvinyl alcohols, polyethylene glycols, polyvinylpyrrolidones, etc.

Preferably, natural polymers or their salts of the polymer component in the grease composition can be selected. In particular, alginates, pectins, celluloses, gelatins and natural starches may be used. Semisynthetic polymers or their salts are distinguished in the base oil or in a grease composition by particularly advantageous properties and therefore constitute a particularly preferred embodiment of the invention. Here, the semisynthetic polymers or their salts are selected from the following group of particular interest:

Cellulose ethers and / or cellulose esters, in particular ethylcellulose, propylcellulose, carboxymethylcellulose (CMC), hydroxypropylcellulose (HPC), hydroxypropylmethylcellulose (HPMC) and cellulose acetate, particularly preferably carboxymethylcellulose (CMC) or a salt thereof, preferably

Sodium salt, or mixtures thereof. Very particular preference is given to the sodium salt of carboxymethylcellulose.

In a preferred embodiment of the invention, the cation of the salt of carboxymethyl cellulose is selected from the group consisting of metals of

1st, 2nd, 3rd or 4th main group or the 12th subgroup or mixtures thereof.

In a particularly preferred embodiment, the following metals are selected from the group consisting of: Li, Na, K, Ca, Ba, Al and / or Zn, particularly preferably from the group consisting of Li, Na, K and

Approximately

In a particularly preferred embodiment, the sodium salt of the carboxymethyl cellulose is Walocel CRT 1000 PA.

Preferred viscosities of the sodium salt of carboxymethyl cellulose are between 10 to 40,000 mPa as a 2% solution in water. Particularly preferably, the molecular weights of the sodium carboxymethylcellulose are in the range between 90,000 g / mol and 700,000 g / mol,

In a preferred embodiment, the semisynthetic polymers of the polymer component are selected from the group consisting of:

Cellulose ethers, cellulose esters, or mixtures thereof. In a particularly preferred embodiment, the thickener component is selected from the group consisting of: soap thickeners, non-soap thickeners or mixtures thereof. With regard to the thickener components soap thickener and

Non-soap thickener distinguished. A general description of thickeners already known to the skilled worker for a long time can be found in T. Goertz, Soap-Based Greases, Composition - Production - Properties, Tribology + Lubrication Technology, Volume 56, 1/2009. In a particularly preferred embodiment, the thickener components of the grease composition according to the invention are selected from the group comprising: metal soaps, complex soaps or mixed soaps which are among the soap thickeners. Among the non-soap thickeners are in particular ureas, clays such as bentonite, montmorillonite or bauxite, silicates, silicas, talc , Polytetrafluoroethylene, metal salts, pigments or graphite. Each of these thickeners can be used singly or in combination.

The "soap thickeners" in lubricating grease compositions are, in particular, metal soaps or salts which can be formed by reaction of metal hydroxides with fatty acids with elimination of water. "Metal hydroxides" are compounds which consist of an ionic crystal lattice in the solid state. The negative lattice units or even anions in this lattice consist of oxygen and hydrogen, in particular hydroxide ions (OH ^" ). The positive lattice units or cations of the lattice are, on the other hand, metals 4th main group and the 12th subgroup.

"Simple metal soaps" are formed by the reaction of metal hydroxide with fatty acid, and in addition to the free fatty acid, triglycerides can also be used

Metal hydroxides are converted, creating soaps with mixed anions.

By contrast, "mixed metal soaps" are understood as meaning mixtures of soaps with various metal ions, in particular cations, which can be formed by reacting two different metal hydroxides with fatty acid Properties of such mixed soap fats composed more or less proportionately from the properties of simple metal soaps. However, mixed metal soaps are preferably used to improve inadequate properties of certain types of soap, for example, to improve the water resistance of lithium and sodium fats by blending with calcium soaps. The preparation is particularly preferably carried out in a one-step process.

"Complex soaps" are generated in particular by the reaction of metal hydroxide with fatty acid and inorganic acids such as boric acid or short-chain organic monocarboxylic acids, preferably acetic acid or dicarboxylic acids, particularly preferably adipic acid azelaic acid and sebacic acid.

"Bentonites" are clay-containing rocks, the majority of which consists of a three-layer silicate with swelling capacity, preferably montmorillonite, Bentonites may contain, in addition to the main proportion, other accompanying minerals, in particular quartz, mica, feldspar or lime in variable proportions widely known (T. Goertz, Gel and Bentonite Fats - Composition - Properties, Tribology + Lubrication Technology, Volume 56, 2/2009).

The term "silicic acids" is understood as meaning the oxygen acids of silicon, in the sense of the invention it is preferably condensates of monosilicic acid (Si (OH) ₄ ), in particular polysilicic acids.

Soap thickeners are typically composed of one or more anions and one or more cations, and are thus in particular ionic compounds. The cation of the soap thickener is selected in a preferred embodiment of the grease composition according to the invention selected from the group consisting of metals of the 1st, 2nd, 3rd and 4th main group and metals of the 12th subgroup. In a particularly preferred embodiment, the following metals are selected from the group consisting of: Li, Na, K, Ca, Ba, Al and / or Zn, particularly preferably from the group consisting of Li, Na, K and Ca. The anions of the soap thickener are selected in a further particularly preferred embodiment from the group consisting of: saturated C 2 to C 30 mono- and / or dicarboxylic acids, mono- or polyunsaturated C 2 to C 30 mono- and / or dicarboxylic acids, aromatic C 5 to C 30 mono- and dicarboxylic acids or a mixture of such carboxylic acids.

In a preferred embodiment, the anions of the soap thickener are selected from monocarboxylic acids. In a further preferred embodiment, the anions of the soap thickener are selected from dicarboxylic acids. Particularly preferred are the anions of the selected from mixtures of mono- and dicarboxylic acids.

In particular, the anions of the soap thickener are selected from the group consisting of: saturated C 2 to C 30 mono- and / or dicarboxylic acids, preferably C 12 to C 20 mono- and / or dicarboxylic acids, particularly preferably stearic acid, sebacic acid, adipic acid, oleic acid and azelaic acid or mixtures thereof.

In addition to the respective monocarboxylic acids and / or dicarboxylic acids, the anions of the soap thickener are preferably selected from derivatives of the monocarboxylic acids and / or dicarboxylic acids. Substituted mono- and / or dicarboxylic acid derivatives, very particularly preferably stearic acid derivatives, oleic acid derivatives and / or sebacic acid derivatives as anions of the soap thickener, are also preferably selected.

In a particularly preferred embodiment of the invention, the mono- and / or dicarboxylic acids are in particular selected from the group consisting of: hydroxystearic acids and / or hydroxystearic acid derivatives, hydroxysebacic acids and / or hydroxysebacic acid derivatives, in particular from 12-hydroxystearic acid.

The term of carboxylic acids therefore includes here in addition to the unsubstituted carboxylic acids and the carboxylic acids with a substituted alkyl group and carboxylic acid derivatives. Preferred substituents of the alkyl group here are selected from the group consisting of: hydroxides, halides, ethers and amines. Preferred carboxylic acid derivatives are selected from the group consisting of: carboxylic acid amides, carboxylic esters,

Carboxylic acid halides, and carboxylic acid anhydrides.

In a further embodiment, the anions of the soap thickener may be selected from the group consisting of inorganic acids, in particular boric acids or phosphoric acids.

In a preferred embodiment, the soap thickener is obtainable in the grease composition by contacting a mono- and / or dicarboxylic acid, preferably the abovementioned and alkanolamines and / or alkylamines, preferably alkanolamines, particularly preferably triethanolamine.

It has also been found that soap thickeners with particularly favorable properties can be obtained by combining a mixture of alkanolamines and one or more metal hydroxides and the mono- and / or dicarboxylic acids according to the invention, which are defined as herein.

In a particularly preferred embodiment, grease compositions are obtainable by contacting a base oil containing water and one and / or more cellulose esters, preferably carboxymethylcelluloses and / or salts thereof, more preferably sodium carboxymethylcellulose, and a thickener component obtainable by contacting a mixture of alkanolamines, especially triethanolamine and one or more metal hydroxides, preferably from the group consisting of lithium, sodium, potassium and calcium hydroxide, in particular potassium hydroxide, and one or more mono- and / or dicarboxylic acids, preferably from the group consisting of stearic acid, 12-hydroxystearic acid, sebacic acid , Oleic acid or mixtures thereof.

In a particularly preferred embodiment, grease compositions are obtainable by contacting a base oil consisting of water and sodium carboxymethylcellulose, a thickener component obtainable by combining a mixture of triethanolamine, potassium hydroxide and stearic acid. Further, the grease compositions of the invention may be prepared by contacting a base oil consisting of water and sodium carboxymethyl cellulose and a thickener component obtainable by combining a mixture of a metal hydroxide, especially a lithium, sodium, potassium, and / or calcium hydroxide, and a mono- and /or

Dicarboxylic acid, preferably stearic acid, stearic acid derivatives, terephthalic acid or terephthalic acid derivatives, sebacic acid or sebacic acid derivatives, adipic acid or adipic acid derivatives, azelaic acid or azealic acid derivatives, oleic acid or oleic acid derivatives or mixtures thereof.

In a particularly advantageous embodiment, these grease compositions are obtainable by contacting a base oil containing water and a carboxymethylcellulose and / or salts thereof, in particular sodium carboxymethylcellulose, and a

Thickener component obtainable by combining alkanolamines, in particular triethanolamine and stearic acid and / or sebacic acid. In another embodiment, such

Lubricating grease compositions are prepared which have a thickener, wherein the thickener is obtainable from one or more mono- or multiisocyanates, preferably diisocyanates, in particular toluene diisocyanate and / or methylene diphenyl isocyanate or dimers thereof, with an amine of the general formula R ' ₂ NR and / or a diamine the general formula R ' ₂ N-

RN-R ' ₂ , wherein R is an aryl, alkyl, or alkylene radical, in particular a polyaryl, polyalkyl or polyalkylene radical, or with a mixture of amines or diamines. "Multiisocyanates" comprise not only integer multiples of the isocyanates, preferably di-, tri-, tetraisocyanates, in particular also oligo- or polyisocyanates, but also half-integer multiples of the isocyanates, or mixtures thereof In a preferred embodiment, the thickener contains the reaction product of one or more diisocyanates with a primary amine. In particular, the grease compositions of the invention may be prepared by contacting a base oil consisting of water and sodium carboxymethylcellulose and a thickener component obtainable by combining a mixture of one or more diisocyanates, preferably aryl diisocyanates, especially toluene diisocyanate and / or methylene diphenylisocyanate, with an alkylamine, preferably a C1 to C10 alkylamine, Octylamine and / or an alkylenediarylamine, in particular methylenedianiline or with a mixture of amines or diamines, are particularly preferably prepared.

By the term "alkyl group" is meant a saturated hydrocarbon chain, and according to the invention, alkyl groups have in particular the general formula -C _n H _2n + i.

"Alkenyl groups" denote hydrocarbon chains which contain at least one double bond along the chain. For example, an alkenyl group having one double bond has, in particular, the general formula - C _n H _2n -i However, alkenyl groups may also have more than one double bond.

"Aryl groups" refer to monocyclic (eg, phenyl), bicyclic (eg, indenyl, naphthalenyl, tetrahydronaphthyl, or tetrahydroindenyl) and tricyclic (eg, fluorenyl, tetrahydrofluorenyl, anthracenyl, or tetrahydroanthracenyl) ring systems in which the monocyclic ring system or at least one of the rings in a bicyclic or tricyclic ring system is aromatic.

Grease compositions can be described by the so-called consistency index (NLGI class, National Lubricating Grease Institute). The classification ranges from 000 to 6. The grease compositions of the invention are preferably in the range of NLGI 000 and NGLI 4, preferably in the range between NLGI 0 and NLGI 3, more preferably have a consistency index of NLGI 2.

The "consistency" is a measure of the inertia of the fat, so the resistance of the fat to change in shape Penetration test can be determined. According to the invention, the "cone penetration" method is preferably used in accordance with DIN ISO 2137. Penetration is understood to be the penetration depth of a defined cone at 25 ° C. after 5 seconds due to its weight force It can therefore serve to classify the fat into consistency classes.

In a preferred embodiment of the lubricating grease composition, the measured penetration in the range from 475 to 170 tenths of a millimeter, preferably in the range between 385 and 220, more preferably in the range between 295 and 265.

In addition to penetration to classify the consistency of grease compositions, flow pressure can also be used to classify grease compositions. This gives information about the mobility of a grease at different temperatures. "Flow pressure" refers to the differential pressure to the atmospheric pressure required to force a grease train out of a test nozzle.The thus determined flow pressure characterizes the flow behavior of the grease compositions according to the invention.The flow pressure can be determined according to DIN 51805-2.

In a preferred embodiment of the invention, the flow pressure, measured at 20 ° C., of the lubricant composition is in the range between 60 and 90 mbar, in particular at 75 mbar. In a further preferred embodiment, the flow pressure of the lubricant composition measured at 0 ° C. is in the range between 85 and 15 mbar, in particular at 100 mbar.

In a further preferred embodiment, the flow pressure of the lubricant composition measured at -5 ° C. is in the range between 135 and 165 mbar, in particular at 150 mbar. In a preferred embodiment, the flow pressure of the lubricant composition measured at -10 ° C. is in the range between 200 and 250 mbar, in particular at 225 mbar. In a preferred embodiment, the flow pressure measured at -20 ° C is the Lubricant composition in the range between 500 and 600 mbar, in particular at 550 mbar.

In a particularly preferred embodiment of the grease composition according to the invention, the electrical conductivity lies in the range between 10 ^-12 and 10 ^-3 S / cm, preferably in the range between 10 ^-9 and 10 ^-3 S / cm, more preferably in the range between 10 ^-7 and 10 ^"5 , in particular in the range between 10 ^{" 5} and 10 ^"3 S / cm. The conductivity is preferably determined on the basis of ISO 16773-1.

In a particularly preferred embodiment, the base oil for producing the lubricating grease composition according to the invention consists of water and a polymer component which can be used according to the invention, in particular cellulose ethers and salts thereof. Very particular preference is given to the sodium salt of carboxymethylcellulose.

In a further embodiment of the invention, the base oil has a water content of 100 wt .-%, preferably of at least 80 wt .-%, 50 and 60, more preferably of at least 30 wt .-% to.

In a preferred embodiment of the invention, the base oil has a viscosity index of at least 120, preferably of at least 140, particularly preferably of at least 180. The "viscosity index" describes the temperature-dependent change in the viscosity of a lubricant and can be determined from the kinematic viscosity according to ISO 3104.

The viscosity of the base oil at 40 ° C is advantageously in a range of 1 and 100,000 mm ² / s, preferably in the range of 1 to 10,000 mm ² / s, more preferably in the range of 100 to 1500 mm ² / s.

In a preferred embodiment, the base oil has a pour point of> 0 ° C., preferably> -5 ° C., in particular of> -10 ° C., more preferably of> -20 ° C., very particularly preferably of> -50 ° C. The "pour point" is a liquid product, the temperature at which the product just flows when cooled

Pour point of -10 ° C on, it means that the composition is at -10 ° C just flowing, at a lower temperature, the composition is, however, frozen. The pour point can be determined according to ISO 3016.

In a particularly preferred embodiment, the composition of water and a polymer component defined according to the invention, preferably in particular cellulose ethers and salts thereof, is used to prepare a lubricating grease composition having one or more of the following properties:

an electrical conductivity in the range between 10 ^"7 and 10 ^{" 3} S / cm,

- a consistency index (NLGI class) of 2

- a walk penetration in the range of 295 and 265

- a flow pressure of 75 mbar at 20 ° C

- a flow pressure of 100 mbar at 0 ° C.

In a further preferred embodiment, the base oil of water and a polymer component defined according to the invention, preferably in particular cellulose ethers and salts thereof, is used to prepare a lubricating grease composition, the base oil having a wider number of the following properties:

- A viscosity in the range of 500 to 1500 mm ² / s

- a pour point of> 0 ° C

- a viscosity index of at least 180.

The most preferred polymer component for these preferred compositions is the sodium salt of carboxymethylcellulose.

Even more preferred is the use of the base oil as defined herein to prepare the lubricating grease composition of the present invention.

For further characterization of the lubricating grease compositions according to the invention, further parameters can be determined. In this case, the following parameters can preferably be determined:

the welding force the wear characteristic

the corrosion properties against copper and aluminum.

The term "welding force" is understood to mean a test force in Newton (N) in which a movement inability, in particular by welding of the four-ball system, occurs in the testing device.

The "Gutkraft" refers to the measured in Newton (N) measured before reaching the welding force at which no immobility, in particular no welding of the four-ball system has occurred in the tester.

The "VKA welding force" here refers to the testing forces for good and welding force in Newton (N), determined according to the conditions according to DIN 51350-4.

Preferably, the process for producing a lubricating grease composition according to the invention comprises the following steps:

(i) providing a base oil from a mixture consisting of water and one or more water-soluble polymers;

(iia) contacting the base oil with at least one thickener

(iii) optionally heating the mixture

(iv) optionally adding additives

In principle, additives may be added to the grease compositions, additives and additives of the invention as known in the art of lubricant compositions. For example, in addition to corrosion inhibitors, emulsifiers, stabilizers, solubilizers and so-called. Extreme Pressure Additives (EP additives) can be used.

In a particularly preferred embodiment, the process for producing a lubricating grease composition according to the invention comprises the following steps:

(i) providing a base oil from a mixture consisting of water and one or more water-soluble polymers; (iia) contacting the base oil with at least one thickener, wherein the at least one thickener has a dropping point of at most 300 ° C, preferably of at most 280 ° C, particularly preferably of 260 ° C or

(iib) contacting the base oil with at least one thickener, wherein the at least one thickener has a melting point of more than 260 ° C, preferably more than 280 ° C, particularly preferably more than 300 ° C;

(iii) optionally heating the mixture;

(iv) optionally adding additives.

A preferred embodiment is a process for preparing a grease composition comprising the steps of:

(i) providing a base oil from a mixture consisting of water and one or more water-soluble polymers,

(iia) contacting the base oil with at least one thickener, wherein the at least one thickener has a dropping point of at most 300 ° C, preferably of at most 280 ° C, particularly preferably of 260 ° C;

(iii) optionally heating the mixture;

(iv) optionally adding additives.

A particularly preferred embodiment describes a process for preparing a grease composition comprising the following steps:

(ii) contacting the base oil with at least one thickener,

wherein the thickener in the base oil is prepared in-situ by contacting at least two thickener-forming components;

(iii) optionally heating the mixture;

(iv) optionally adding additives

Particularly preferred is a process for the preparation

A grease composition comprising the following steps: (i) providing a base oil from a mixture consisting of water and one or more water-soluble polymers;

(ii) contacting the base oil with a thickener, wherein the thickener in the base oil is prepared in-situ by contacting at least two thickener-forming components, preferably one or more

Metal hydroxides, particularly preferably from the group consisting of lithium, sodium, potassium, and calcium hydroxide, in particular potassium hydroxide,

(iii) optionally heating the mixture to 40 to 90 ° C, in particular 60 to 80 ° C,

(iv) adding one or more mono- and / or dicarboxylic acids, preferably from the group consisting of stearic acid, 12-hydroxystearic acid,

Sebacic acid, oleic acid or mixtures thereof.

(v) optionally heating the mixture;

(vi) optionally adding additives. In particular, the process for producing a

Grease composition, in another preferred embodiment, the following steps:

(ii) contacting the base oil with the thickener, wherein the thickener in the

Base oil is prepared in situ by contacting at least two components forming the thickener;

(iii) optionally heating the mixture;

(iv) optionally adding additives.

In the case of soap thickeners, one component is a metal hydroxide, or an alkyl or alkanolamine, the second component is a carboxylic acid according to the invention. In the case of polyureas, one component is a diisocyanate, the second

Component of an inventive amine.

In the case of in situ production of soap thickeners, it is advantageous to provide the base (eg, a metal hydroxide) in the base oil and then to heat the mixture first. These are temperatures of 40 to 90 ° C, especially preferably from 60 to 80 ° C advantageous. Only then does the addition of the fatty acids, preferably of mono- and / or dicarboxylic acids, take place.

In the in-situ production of soaps according to the invention, metal hydroxides from the group consisting of lithium, sodium, potassium and calcium hydroxide, in particular potassium hydroxide, are of particular interest.

In the compositions according to the invention, in the processes and in the base oil according to the invention and in the uses of this base oil, carboxymethyl cellulose is particularly preferred as the polymer component, the sodium salt of carboxymethyl cellulose being particularly preferred.

In a particular aspect, the invention relates to lubricant compositions comprising water and a first component of one or more thickeners or salts thereof (thickener component) and a second component of one or more natural or chemically modified polymers or salts thereof (polymer component), wherein the thickener is obtainable by contacting a mono- or dicarboxylic acid or mixtures thereof and alkanolamines, alkylamines or mixtures thereof.

Unless expressly stated otherwise below, the above definitions apply equally to this particular aspect of the invention.

These grease compositions have the particular advantage that the thickener component can form ionic surfactant complexes with the polymer component. These can additionally have a positive effect on the lubricating performance.

The use of amines to form the thickener component has the advantage that at the same time the biostatic effect known from amines can be used. This makes it possible to reduce or even eliminate the use of biocides in the composition. Amines can also provide the composition with additional corrosion protection. The use of further corrosion inhibitors can thus be reduced. Amines, especially triethanolamine, also have buffering properties. The use of amines in the thickener component can therefore buffer the pH of the grease composition and thus increase the stability of the composition.

In a particularly preferred embodiment of the invention, the amines are trialkanolamines, preferably selected from the group consisting of triethanolamine, tripropanolamine, tributanolamine or mixtures thereof. Particularly preferred is triethanolamine.

Preferably, monocarboxylic acids are used to form the thickener component. The monocarboxylic acid is preferably selected from the group consisting of saturated monocarboxylic acids or monounsaturated monocarboxylic acids, more preferably myristic acid, myristic acid derivatives, palmitic acid, palmitic acid derivatives, margaric acid, margarine acid derivatives,

Stearic acid, stearic acid derivatives, eicosanoic acid, eicosanoic acid derivatives, palmitoleic acid, palmitoleic acid derivatives, oleic acid, oleic acid derivatives, elaidic acid, elaidic acid derivatives, icosenoic acid, icosenic acid derivatives, cetoleic acid cetoleic acid derivatives or mixtures thereof, particularly preferably stearic acid, stearic acid derivatives, oleic acid, oleic acid derivatives or mixtures thereof, in particular stearic acid, 12-hydroxystearic acid, Oleic acid or mixtures thereof. Particularly preferred is stearic acid or 12-hydroxystearic acid. In a very particularly preferred embodiment, the thickener is obtainable by combining a monocarboxylic acid, preferably stearic acid or 12-hydroxystearic acid, with alkanolamines, in particular with trialkanolamines. Particularly preferred is triethanolamine. About a variation of the thickener concentration, the consistency measures

(NLGI class) can be set in the range between NLGI 000 and NGLI 4, preferably the consistency index is in the range between NLGI 0 and NLGI 3, particularly preferred in NLGI 2.

In the case of a thickener obtainable by combining stearic acid and triethanolamine, in a particularly preferred Embodiment, the NLGI class of 2 can be adjusted by the addition of 30 to 35 wt .-% stearic acid and 15 to 20 wt .-% triethanolamine.

The polymer component is preferably selected from the group consisting of salts of modified cellulose ethers, preferably salts of carboxymethylcellulose, in particular sodium carboxymethylcellulose.

The polymer component serves primarily to vary the viscosity of the base oil. The viscosity can be 1 to 100,000 mm 2 / s at 40 ° C., preferably 1 to 10,000 mm 2 / s, particularly preferably 100 to 1,500 mm 2 / s.

In a preferred embodiment of this aspect of the invention, the relative proportion of water is at most 70% by weight, preferably at most 50% by weight, particularly preferably at most 40% by weight, very particularly preferably at most 35% by weight, if the Thickener component has a dropping point of not more than 260 ° C, preferably of at most 280 ° C, particularly preferably of 300 ° C.

In an alternative embodiment of this aspect of the invention, the maximum amount of water is in the range of 10 to 95 wt .-%, preferably in the range of 20 to 70 wt .-%, particularly preferably in the range of 30 to 50 wt .-%.

The lubricant composition according to this aspect of the invention may additionally contain one or more synthetic polymers. In this case, the relative proportion of the synthetic polymer (or synthetic polymers) in the overall composition is less than 5% by weight, especially at most 4.5% by weight, more preferably at most 3% by weight, still more preferably at most 1, 5 wt .-%, in particular at most 0.5 wt .-% is.

The synthetic polymer is preferably selected from the group consisting of polyvinyl alcohols, pyrolidones, aliphatic polyethers. Preferred are polyethylene glycol, polypropylene glycol or mixtures thereof, more preferably polyethylene glycol, more preferably polyethylene glycol having a molecular weight in the range of 600 to 10,000,000 Da, especially polyethylene glycol having a molecular weight in the range of 10,000 to 1,000,000 Da. Lubricating grease compositions containing salts of carboxymethylcellulose, in particular sodium carboxymethylcellulose, and polyethylene glycol, in particular polyethylene glycol having a molecular weight in the range of 10,000 to 1,000,000, as polymer component and a thickener obtainable by combining stearic acid and trialkanolamines (in particular

Triethanolamine) are particularly preferred.

The grease compositions may additionally contain commercial antifreeze. This may serve to adjust the freezing point, vapor pressure or pour point of the composition. The

Antifreeze is preferably selected from the group consisting of polyhydric alcohols, salts or ionic liquids, more preferably glycerol. It may be present in a relative proportion of not more than 60% by weight, preferably not more than 30% by weight, more preferably not more than 15% by weight, in particular not more than 10% by weight, in the lubricating grease composition.

In one embodiment of the invention, the lubricant compositions may also contain a commercial corrosion inhibitor. This is preferably selected from the group consisting of triazoles, thiadiazoles, amine and alkali salts of sulfonates, phosphonates, thiophosphonates, carboxylic acids or mixtures thereof.

In addition, the lubricant composition can be added in a further embodiment of the invention, a commercially available emulsifier.

The emulsifiers are preferably selected from the group consisting of organophosphates, fatty acid glycol ethers, Alkylpolyglykolethercarbonsäuren or mixtures thereof.

Particularly preferred lubricant grease compositions according to an alternative embodiment of the invention contain the following components: Table 1

^* each in wt .-% based on the total grease composition

In an alternative embodiment, the compositions may contain the following components:

Table 2

This results in very particularly preferred compositions (formulations) from the components of Table 1 or 2 in combination with an appropriate amount of water (ad 100 wt .-%). By way of example, Example 1 is given for an embodiment of Table 2.

In an alternative particularly preferred embodiment, the grease composition of the invention contains the following components Table 3

Example 10 below is exemplary of this embodiment of the invention.

General manufacturing process

Formulation of the grease compositions of the invention

Example 1 - Preparation of a Lubricating Grease Composition According to the Invention

Preparation of the base oil

A mixture of 22.5 g of sodium carboxymethylcellulose and 0.5 g of polyethylene glycol (Mw ~ 90,000 g / mol) are dissolved in 322.0 g of water.

Preparation of grease composition

17.5 g of potassium hydroxide (KOH) and 174.0 g of triethanolamine are dissolved in 322.0 g of base oil. 328 g of stearic acid are added with stirring. The reaction product is stirred at room temperature for 15 minutes. 15.0 g of corrosion inhibitor, 83.5 g of glycerol and 37.0 g of emulsifier are added. Subsequently, the mixture is homogenized by rolling.

6 stearic acid 32.8

7 corrosion inhibitor 1, 5

8 glycerol - 86.5% 8.35

9 emulsifier 3.7

The grease was examined according to the standardized procedures. The resulting grease had the following excellent properties:

For the following examples, a base oil mixture according to the invention is used which consists of a mixture of 160 g of sodium carboxymethylcellulose and 9840 g of water.

Example 2 - Grease composition with a simple lithium metal soap

6.7 g of lithium hydroxide are dissolved in 453.2 g of the base oil mixture at 60 ° C. 40.1 g of stearic acid are added with stirring. The reaction product is heated to 80 ° C and held at the temperature for 15 minutes. The mixture is homogenized by rolling.

Example 3 - Grease composition with a simple calcium metal soap

30 g of calcium hydroxide (Ca (OH) 2 ^* 2H 2 O) are dissolved in 349 g of the base oil mixture at 70 ° C. 121 g of 12-hydroxystearic acid are added with stirring. The mixture is homogenized by rolling.

1 water 68.7

sodium

2 1, 1

(CMC)

3 Ca (OH) 2 ^* 2 H 2 O 6.00

4 12-hydroxystearic acid 24.2

Example 4 - Grease composition with a simple barium metal soap

83 g of potassium hydroxide (KOH) are dissolved in 308 g of the base oil mixture at 70 ° C. 154 g of stearic acid are added with stirring. After cooling, rolling the mixture provides a homogenized grease composition.

The grease was examined according to the standardized procedures. The resulting grease had the following properties:

Property measured value

Penetration (DIN ISO

Worked penetration

2137):

234

Class 3 Example 5 - Grease composition with a simple barium metal soap

35 g of barium hydroxide (Ba (OH) 2 ^* H 2 O) are dissolved in 450 g of the base oil mixture at 80 ° C. 99 g of stearic acid are added with stirring. The reaction mixture is stirred for 15 minutes at 80 ° C. Cooling and rolling the mixture provides a homogenized grease composition.

Example 6 - Grease composition with a simple sodium metal soap

22.5 g of sodium hydroxide (NaOH) are dissolved in 318.0 g of the base oil mixture at 70 ° C. 160 g of stearic acid are added with stirring. After cooling, the mixture is homogenized by rolling.

Component% by weight

1 water 62.6

sodium

2 1, 0

(CMC)

3 NaOH 4.5

4 stearic acid 32.0 The grease was examined according to the standardized procedures. The resulting grease had the following excellent properties:

Example 7 - Lubricating grease composition with a lithium complex soap

21 g of lithium hydroxide (LiOH) are dissolved in 386.5 g base oil mixture at 60 ° C. A mixture of 62.5 g of 12-hydrystearic acid and 30 g of sebacic acid is added with stirring. The mixture is heated to 90 ° C and stirred for 15 minutes at this temperature. Cooling and rolling provides a homogenized grease composition.

Example 8 - Grease composition with a sodium complex soap 19.25 g of sodium hydroxide (NaOH) are dissolved in 388.0 g base oil mixture at 60 ° C. A mixture of 62.5 g of 12-hydrystearic acid and 30 g of sebacic acid is added with stirring and heated at 80 ° C for 15 minutes. Cooling and rolling provides a homogenized grease composition.

Example 9 - Grease composition with barium complex soap

41.3 g of barium hydroxide (Ba (OH) 2 ^* H 2 O) are dissolved in 385.0 g of base oil mixture at 70 ° C. A mixture of 47.1 g of stearic acid and 26.6 g of sebacic acid is added with stirring. After cooling, the mixture is homogenized by rolling.

Component% by weight

1 water 75.8

Natriumcarboxymethylcellul

2 1, 2

ose (CMC)

3 Ba (OH) 2 ^* H 2 O 8.3 4 stearic acid 9.4

5 sebacic acid 5.3

Preparation of a lubricant with triethanolamine soap

Example 10

17.4 g of triethanolamine are placed in 220.0 g of base oil mixture at 25 ° C with stirring. 32.8 g of stearic acid are added with vigorous stirring. The mixture is homogenized by rolling.

Property measured value

Penetration (DIN ISO

Worked penetration

2137):

236

NLGI class 3 Making a gelfat

Example 1 1 10.0 g of highly dispersed silicic acid (HDK T40) are initially introduced into 90.0 g of base oil mixture at 25 ° C. with stirring. The mixture is homogenized by rolling.

General implementation of the test methods:

1. Determination of the cone penetration according to DIN ISO 2137

The cone penetration of greases is determined at 25 ° C by loosening the cone device from the penetrometer so that the cone sinks in for 5 seconds. Then the penetration depth is measured.

The cone used is an optional cone according to DIN ISO 2137, consisting of a truncated cone made of brass with removable top made of hardened steel. Optionally, a quarter cone according to DIN ISO 2137 can be used.

The dimensions and limit deviations correspond to Fig. 3 and Fig. 5 to DIN ISO 2137. A) Procedure for resting penetration

The resting penetration is determined on sample quantities which have been filled under light mechanical stress into a container suitable for the test.

Preparing the sample

The samples are taken in accordance with ASTM D 4057. The sample can be checked for inhomogeneity, oil separation, phase transitions or coarse contamination. If different conditions apply, a new sample will be used. A sufficient amount of the sample is withdrawn to overfill the pot of grease kneader.

An empty metal container and another metal container filled with the sample are placed in a water bath according to DIN ISO 2137. The temperature of the sample is brought to 25 ° C and held. The sample is transferred to the metal container of the grease mixer, taking care to stir the sample as little as possible. The container is pushed open to expel any trapped air. The grease is then compacted under low stress with a spatula. Excess grease is removed by pulling the blade of the spatula over the rim of the pot at an angle of about 45 ° to the direction of movement to create a flat surface. During the determination of the rest penetration no further leveling or smoothing of the surface takes place, the measurement is carried out immediately afterwards.

The penetrometer cone is carefully cleaned before each test and held securely in the raised position during cleaning. Any grease or oil residue will be completely removed from the penetrometer shaft.

penetration measurement

The jar is placed on the exactly horizontal penetrometer table, the mechanism is adjusted to hold the cone in the "zero" position, and care is taken with each measurement that the unit is carefully aligned so that the cone tip is in the "zero" position Sample surface just at the Touched point, which is determined depending on the consistency of each sample. The observation took place with the help of the shadow of the cone tip. The pot is centered depending on the nature of the grease by means of a centering device. The cone shaft is quickly released and then it is dropped for 5.0 seconds and then fixed in this position. The indicator shaft is gently pressed down until it is stopped by the cone shaft. Subsequently, the penetration can be read from the display scale.

For samples over 200 units in penetration, the sample will only be used for one test. In the case of a penetration of 200 units or less, three tests are carried out in a single container by setting the penetrations at an angular distance of approximately 120 °, approximately halfway between the center and the wall of the container. A total of three determinations are carried out with a grease sample.

B) Implementation for the Walkpenetration

Swath penetrations are determined immediately after swirling the sample with 60 double strokes in a standard grease mixer.

flex

A sufficient amount of the sample is withdrawn to overfill the pot of grease kneader. The assembled grease mixer is placed in a water bath maintained at 25 ° C until the temperature of the grease kneader and its contents is 20.0 ° C. The grease is then exposed for 1 min 60 double strokes with the piston. The following further experiments were carried out in quick succession.

Preparing the sample

The rolled sample is prepared in the pot for further testing in accordance with DIN ISO 2137.

penetration measurement

The penetration is determined as already described in A).

2. Determination of the NLGI class The National Lubricating Grease Institution (NLGI) classifies greases by their consistency, which is determined with 60 strokes of the walkpenetration. The NLGI classification contains nine consistency classes or classes, each of which corresponds to a specified range of walkpenetration. The NLGI classification is defined in ISO 6743-99 and listed for classes 000 to 4 in the following table:

NLGI class Walkpenetration

in units

(Tenths of a millimeter)

000 445 to 475

00 400 to 430

0 355 to 385

1 310 to 340

2 265-295

3 220 to 250

4 175 to 205

3. Determination of the dropping point of grease compositions

The determination of the dropping point is completely automated according to the requirements of the standard IP 396 by means of a double heating ramp. The grease to be measured is brought to an initial temperature of 10 ° C above ambient temperature. Subsequently, the sample is heated at a heating rate of 10 ° C / min to a starting temperature which depends on the expected dropping point of the sample. Once a temperature is reached which is 20 ° C below the expected dropping point, the heating rate is reduced to 1 ° C / min.

When determining an unknown dropping point for the first time, the approximate determination of the dropping point should first be made. For this purpose, a heating rate of 10 ° C / min over the entire period of the measurement is set. For the determination of the temperature, which is 20 ° C below the expected dropping point, the approximate value of the dropping point can be used. A second measurement provides the dropping point of the grease composition. 4. Determination of the flow pressure of lubricating greases using the Kesternich method according to DIN 51805-2

The grease-filled test nozzle of the tester is connected to a gas pressure generating device and a pressure gauge. At an agreed test temperature, which can be adapted to the particular grease, the pressure is preferably increased at intervals of 30 s by a certain amount, which is dependent on the flow pressure of the grease, so long until the grease train has leaked out of the test nozzle and the compressed gas escapes through the test nozzle.

Tempering the tester

The tempering chamber equipped with the test nozzle is tempered for preferably 2 hours before the start of the test. The samples to be measured are measured at 20 ° C, 0 ° C, -10 ° C and -20 ° C. In this case, the recommended maximum period of time provided for in DIN 51805-2 is preferably maintained until the intended test temperature is reached.

5. Determination of the wear cap according to DIN 51350-5

The grease composition is tested in a four-ball system (DIN 51350-1), which preferably consists of a rotating ball (running ball), which slides under a predetermined test force on three of their same balls (stationary balls). The test time may preferably be 60 minutes or 60 seconds. The dome diameter of the three stationary balls is measured and averaged.

execution

The ball pot or ball holder consisting of clamping, pressure plate and test balls are thoroughly cleaned and dried in a residue-free solvent, preferably FAM gasoline.

The cleaned ball cup is filled free of air bubbles with the grease composition to be tested. Subsequently, three cleaned Prüfkugeln (DIN 51350-1), preferably the stand balls, slightly pressed and firmly clamped. The ball cup is filled so that the stand balls are covered and the ball holder is not immersed in the grease. The excess

Grease composition is preferably applied by means of a spatula over the Subtracted the edge of the ball pot. In particular, the ball pot and grease composition have a temperature between 18 ° C and 40 ° C. Another test ball is pressed as a ball in the ball holder and inserted into the test spindle. After placing the ball pot with the tip of its mandrel on the recess of the turntable, the test force is applied, the test force is preferably set to 150 N, 300 N or 1000 N according to three different methods. In addition, the drive motor is set to 1450 revolutions per minute.

evaluation

To determine the average calotte diameter whose diameter is measured on the stationary balls in the sliding direction and perpendicular to the sliding direction. The arithmetic mean is formed from the individual values obtained in this way.

6. Determination of the welding force according to DIN 51350-4

The lubricating grease compositions according to the invention are tested in a four-ball system (DIN 51350-1), which preferably consists of a rotating ball (running ball), which slides under a specified test force on three identical balls (stationary balls) (analogous to point 5.) The test load can be gradual be increased until a welding of the four-ball system occurs. The test is carried out analogously to the implementation in point 5 (vide supra).

The test load is increased to determine the welding force, however, until a welding of the balls occurs. For this purpose, the test load is increased from test run to test run in the test force range between 2000 N and 4800 N by 200 N in each case or by 500 N in the test load range between 5000 N and 12000 N.

evaluation

The VKA welding force of a grease composition is preferably determined by two matching individual readings from three tests each, for goodness and welding force.

7. Determination of the corrosion properties on copper in accordance with DIN 5181 1 To test the corrosion properties of lubricating greases, rolling bearings, sliding bearings and sliding surfaces in the presence of water under operating conditions are examined. A mechanically ground copper strip or aluminum strip is left in a grease sample for 24 hours. Subsequently, its degree of corrosion is assessed after the discoloration. The test temperature depends on the upper service temperature of the particular grease and can be 50 ° C, 100 ° C and / or another temperature to be agreed.

Preparation of copper / aluminum strip

All surface defects are removed by means of an abrasive paper or with abrasive cloth. Optionally, for this purpose, the abrasive medium placed on a flat surface, wetted with a little solvent and the copper strips are rubbed on it with circular movements. The copper strips are stored under solvent until use. The insertion of the copper strip in the holding device by means of tweezers.

execution

Immediately after its preparation at room temperature, the copper strip or aluminum strip is immersed obliquely in a beaker which was previously filled with the test grease at room temperature up to 10 mm below the edge and preferably free of air bubbles. The copper strip protrudes here preferably 10 mm out of the grease. The test is carried out according to the agreed test duration and / or temperature.

8. Determination of electrical conductivity of lubricating grease compositions

The grease compositions are measured for electrical conductivity testing by the method of impedance spectroscopy following ISO 16773-1. Impedance spectroscopy is a method to study ion transport processes in solids. An alternating voltage, preferably of low amplitude, is applied to the lubricating grease composition to be examined by introducing a sample into an electrochemical cell. The alternating voltage can generate in the sample an alternating current of the same frequency, which is measured by means of a frequency response analyzer.

A corresponding control and evaluation software can be based on the System data, depending on the sample create an equivalent circuit diagram and adjust with the measured frequency changes and thus determine the conductivity of the sample.

Sample preparation and implementation

The grease composition is filtered before each measurement, preferably inert filter materials, in particular ceramics are used and the sample is degassed, preferably, the degassing of the sample can be carried out in an ultrasonic bath at elevated temperature. Thereafter, the respective sample can be filled into a test cell. The sample is heated gradually, preferably in a range between 0 and 150 ° C. Subsequently, the sample is preferably cooled in the same range between 150 and 0 ° C. The electrical conductivity is determined by means of the evaluation software.

9. Determination of the pour point of grease compositions (based on DIN ISO 3016)

The sample vessel is filled with the sample at room temperature up to the ring mark. The sample cup is capped with a cork containing a pour point thermometer. Align the cork and thermometer so that the cork is firmly seated, the thermometer and sample cup coaxial, and that the thermometer cup is submerged until the beginning of the capillary is approximately 3 mm below the oil surface. The sample vessel is placed in the ethanol bath without a jacket vessel. For oils that are expected to have a pour point below -15 ° C, the sample is cooled down to 0 ° C in large increments. Thereafter, the sample is further cooled in 3 ° C increments. In these intervals, it is checked whether the oil is still flowable. It is tested up to the temperature at which no movement of the sample is observed after 5s in a horizontal position. 10. Determination of the Viscosity Index of Lubricating Grease Compositions To determine the viscosity index, the kinematic viscosities are carried out in accordance with the respective implementation in DIN 51562-1. The kinematic viscosities are determined at 40 ° C and 25 ° C. The calculation of the viscosity index is carried out according to a corresponding

Evaluation software, taking into account the kinematic viscosities at 40 and 25 ° C.

A u s f o rs a m e n s

Embodiment 1

A lubricant composition containing water and a first component of one or more thickeners or salts thereof (thickener component), wherein

a) the relative proportion of water is at most 70% by weight, preferably at most 50% by weight, particularly preferably at most 40% by weight, very particularly preferably at most 35% by weight, if the thickener component has a dropping point of at most 260 ° C, preferably of at most 280 ° C, particularly preferably of 300 ° C; or b) the relative proportion of water is at most 40% by weight, preferably at most 35% by weight, if the thickener component has a melting point of more than 260 ° C, preferably more than 280 ° C, particularly preferably more than 300 ° C having.

Embodiment 2:

A lubricant composition according to embodiment 1, wherein a) the relative amount of water is at least 10% by weight, preferably at least 15% by weight, more preferably at least 20% by weight, most preferably at least 30% by weight, if the Thickener component has a dropping point of not more than 260 ° C, preferably of at most 280 ° C, particularly preferably of 300 ° C; or b) the relative proportion of water is at least 20% by weight, preferably at least

25 wt .-%, particularly preferably at least 30 wt .-% is when the Thickener component has a melting point of more than 260 ° C, preferably more than 280 ° C, more preferably more than 300 ° C.

Embodiment 3:

A lubricant composition containing water and a first component of one or more thickeners or salts thereof (thickener component) according to any one of embodiments 1 or 2, wherein the lubricant composition contains a second component of one or more water-soluble polymers or salts thereof (polymer component).

Embodiment 4:

A lubricant composition according to embodiment 3, wherein the relative proportion of the polymer component in the total composition is 0.05 to 15, preferably 0.1 to 10, especially 0.1 to 5 wt .-%.

Embodiment 5:

Lubricant composition according to one of the preceding embodiments 3 or 4, wherein the weight ratio of the polymer component to the thickener component is between 1:60 and 1: 2, preferably between 1:40 and 1: 3, in particular between 1: 30 and 1: 5.

Embodiment 6:

A lubricant composition according to any one of the preceding embodiments, wherein the relative proportion of the thickener component to the total composition is at least 20% by weight, preferably at least 30% by weight, more preferably at least 35% by weight, most preferably more than 35% by weight ,

Embodiment 7:

A lubricant composition according to any one of the preceding embodiments 3 to 6, wherein the relative proportion

The water between 25 and 95% by weight,

• the polymer component between 0.5 and 4.0 wt .-% and

The thickener component is between 5 and 70% by weight,

compared to the total composition. Embodiment 8

A lubricant composition according to any one of the preceding embodiments 3 to 7, wherein the polymers of the polymer component are selected from the group consisting of: a) natural polymers such as polysaccharides, inorganic polysaccharides, natural rubbers and lignins;

b) chemically modified polymers such as cellulose ethers, cellulose esters and modified starches;

c) synthetic polymers such as polyvinyl alcohols, polyethylene glycols,

polyvinylpyrrolidones; or mixtures thereof. Embodiment 9:

A lubricant composition according to any of preceding embodiments 3 to 8, wherein the natural polymers of the polymer component are selected from the group consisting of:

Alginates, pectins, celluloses, gelatins and natural starches.

Embodiment 10:

A lubricant composition according to any one of the above embodiments 3 to 9, wherein the semisynthetic polymers of the polymer component are selected from the group consisting of:

Cellulose ethers and / or cellulose esters, in particular ethylcellulose,

Propylcellulose, carboxymethylcellulose (CMC), hydroxypropylcellulose (HPC), hydroxypropylmethylcellulose (HPMC) and cellulose acetate, particularly preferably carboxymethylcellulose (CMC) or a salt thereof, preferably the sodium salt, or mixtures thereof.

Embodiment 1 1:

A lubricant composition according to any one of the preceding embodiments, wherein the thickener component is selected from the group consisting of: soap thickeners, in particular simple metal soaps, complex soaps and / or mixed metal soaps, non-soap thickeners, in particular ureas, clays, in particular bentonite, montmorillonite or bauxite, silicates, silicas, talc, polytetrafluoroethylene, metal salts, pigments, graphite or mixtures thereof.

Embodiment 12:

Lubricant composition according to embodiment 1 1, wherein the soap thickener contains a cation, wherein the cation is in particular selected from the group consisting of: metals of the 1st, 2nd, 3rd and 4th main group and metals of the 12th subgroup, preferably from the group consisting of Li, Na, K, Ca, Ba, Al and / or Zn, particularly preferably from the group consisting of Li, Na, K and Ca.

Embodiment 13:

A lubricant composition according to any one of the preceding embodiments 1 1 or 12, wherein the anions of the soap thickener are selected from the group consisting of: saturated C 2 to C 30 mono- or dicarboxylic acids, mono- or polyunsaturated C 2 to C 30 mono- or dicarboxylic acids, aromatic C 5 to C 30 Mono- and dicarboxylic acids or a mixture of such carboxylic acids, preferably from the group consisting of saturated C2 to C20 mono- or dicarboxylic acids, mono- or polyunsaturated C2 to C20 mono- or dicarboxylic acids, aromatic C5 to C30 mono- and dicarboxylic acids or

Mixtures thereof, particularly preferably from the group consisting of stearic acid, sebacic acid, 12-hydroxystearic acid, adipic acid and azelaic acid, terephthalic acid or mixtures thereof. Embodiment 14:

Lubricant composition according to embodiment 1 1, wherein the thickener is obtainable from one or more mono or multiisocyanates, preferably diisocyanates, in particular toluene diisocyanate and / or methylene diphenyl isocyanate or dimers thereof, with an amine of the general formula R ' ₂ NR and / or a diamine of the general formula R ' ₂ NRN-R'2, wherein R is an aryl, alkyl, or

Allkylenrest, in particular a polyaryl, polyalkyl or a polyalkylene radical, or with a mixture of amines or diamines, preferred are primary amines.

Embodiment 15:

A lubricant composition according to any of the above embodiments 1 1 to 14, wherein the thickener component is obtainable by contacting Water, a thickener component according to claim 1 1, in particular a soap thickener defined according to claims 12 or 13 and alkanolamines and / or alkylamines, preferably alkanolamines, particularly preferably triethanolamine.

Embodiment 16:

Lubricant composition according to one of the preceding embodiments, wherein the consistency index (NLGI class) is in the range between 000 and 4, in particular 2.

Embodiment 17:

A lubricant composition according to any one of the preceding embodiments, wherein the walk penetration is in the range between 475 and 170 tenths of a millimeter, preferably in the range between 385 and 220, more preferably in the range between 295 and 265.

Embodiment 18:

Lubricant composition according to one of the preceding embodiments, wherein the electrical conductivity in the range between 10 ^"12 and 10 ^{" 3} S / cm, particularly preferably in the range between 10 ^"9 and 10 ^{" 3} S / cm, very particularly preferably in the range between 10 ^"7 and 10 ^"3 S / cm, especially in the range between 10 ^{" 5} and 10 ^"3 S / cm.

Embodiment 19:

Base oil for the preparation of a lubricant composition, wherein it contains water and a polymer component defined according to one of the Auführungsformen 3 to 5 and 7 to 10, preferably consists thereof.

Embodiment 20:

Base oil according to embodiment 19, wherein it has a water content of 100 wt .-%, preferably of at least 80 wt .-%, particularly preferably of at least 30 wt .-%.

Embodiment 21: Base oil according to one of the embodiments 19 or 20, wherein the base oil has a viscosity index of at least 120, preferably of at least 140, particularly preferably of at least 180. Embodiment 22:

Base oil according to one of embodiments 19 to 21, wherein the base oil at 40 ° C has a viscosity in the range between 1 and 100,000 mm ² / s, preferably in the range between 1 to 10,000 mm ² / s, more preferably in the range between 1 to 1500 mm ² / s.

Embodiment 23:

Base oil according to one of embodiments 19 to 22, having a pour point of> 0 ° C., preferably> -5 ° C., in particular of -10 ° C., more preferably of -20 ° C., very particularly preferably of> -50 ° C on.

Embodiment 24:

A lubricant composition containing a base oil according to any one of Embodiments 19 to 23. Embodiment 25:

Use of a composition of water and a polymer component defined according to any of embodiments 3 to 18 or the base oil defined in any of embodiments 19 to 23 for the preparation of a lubricant composition.

Embodiment 26:

Process for preparing a lubricant composition comprising the following steps:

(iia) contacting the base oil with at least one thickener

(iii) optionally heating the mixture

(iv) optionally adding additives.

Embodiment 27: A process for preparing a grease composition according to embodiment 26, comprising the following steps:

(Ub) bringing together the base oil with at least one thickener, wherein the at least one thickener has a melting point of more than 260 ° C, preferably more than 280 ° C, more preferably more than 300 ° C;

(iii) optionally heating the mixture;

(iv) optionally adding additives.

Embodiment 28:

Process for the preparation of a grease composition according to

Embodiments 26 or 27 comprising the following steps:

(ii) contacting the base oil with at least two reactive thickener precursors, wherein the thickener may optionally be prepared in-situ by contacting the at least two reactive thickener precursors;

(iii) optionally heating the mixture;

(iv) optionally adding additives. Embodiment 29:

A process for producing a lubricating grease composition according to any one of embodiments 26 to 28, comprising the following steps:

(ii) contacting the base oil with a reactive thickener precursor, preferably with one or more metal hydroxides, particularly preferably from the group consisting of lithium, sodium, potassium, and calcium hydroxide, in particular potassium hydroxide,

(iv) optionally adding additives.

Claims

Patent claims

A lubricant composition comprising water and a first component of one or more thickeners or salts thereof (thickener component) and a second component of one or more natural or chemically modified polymers or salts thereof (polymer component), characterized in that the thickener is obtainable by combining a mono- or dicarboxylic acid or mixtures thereof and alkanolamines, alkylamines or mixtures thereof.

2. Lubricant composition according to claim 1, characterized in that the relative proportion of water is at most 70% by weight, preferably at most 50% by weight, particularly preferably at most 40% by weight, very particularly preferably at most 35% by weight. is when the thickener component has a dropping point of at most 260 ° C, preferably of at most 280 ° C, particularly preferably of 300 ° C.

3. Lubricant composition according to claim 1 or 2, characterized in that the relative proportion of the polymer component in the total composition 0.05 to 15 wt .-%, preferably 0.1 to 10 wt .-%, in particular 0.1 to 5 wt. -% is.

4. Lubricant composition according to one of the preceding claims, characterized in that the relative proportion of the thickener component in the total composition of at least 20 wt .-%, preferably at least 30 wt .-%, more preferably at least 35 wt .-%, most preferably more than 35 Weight%.

5. Lubricant composition according to one of the preceding claims, characterized in that the weight ratio of the polymer component to the thickener component is between 1:60 and 1: 2, preferably between 1:40 and 1: 3, in particular between 1: 30 and 1: 5.

6. Lubricant composition according to claim 1, characterized in that the maximum proportion of water in the range of 10 to 95 wt.%, Preferably in Range of 20 to 70 wt .-%, particularly preferably in the range of 30 to 50% by weight.

7. Lubricant composition according to claim 1, characterized in that the relative proportion

The water between 25 and 95% by weight,

• the polymer component between 0.5 and 4.0 wt .-% and

The thickener component is between 5 and 70% by weight of the total composition.

8. A lubricant composition according to any one of the preceding claims, characterized in that the polymer component is selected from the group consisting of: a) natural polymers such as polysaccharides, inorganic polysaccharides, natural rubbers and lignins;

b) chemically modified polymers such as cellulose ethers, cellulose esters and modified starches; or mixtures thereof.

9. Lubricant composition according to one of the preceding claims, characterized in that it additionally contains one or more synthetic polymers.

10. The composition according to claim 9, characterized in that the relative proportion of the synthetic polymer in the total composition less than 5 wt .-%, at most 4.5 wt .-%, at most 3 wt .-%, more preferably at most 1, 5 Wt .-%, in particular at most 0.5 wt .-% is.

1. The composition according to any of the preceding claims 9 or 10, characterized in that the synthetic polymer is selected from the group consisting of aliphatic polyethers, preferably polyethylene glycol, polypropylene glycol or mixtures thereof, more preferably polyethylene glycol, more preferably polyethylene glycol of approximate molecular weight Area from 600 to 10,000,000, especially polyethylene glycol of approximate molecular weight in the range of 10,000 to 1,000,000.

12. A lubricant composition according to any one of the preceding claims, characterized in that the chemically modified polymers of the polymer component are selected from the group consisting of cellulose ethers, cellulose esters, or mixtures thereof.

13. A lubricant composition according to any one of the preceding claims, characterized in that the thickener contains a cation, wherein the cation is selected from the group consisting of: metals of the 1st, 2nd, 3rd and 4th main group and metals of the 12th subgroup ,

14. A lubricant composition according to any one of the preceding claims, characterized in that the anions of the thickener are selected from the group consisting of: saturated C2 to C30 mono- or dicarboxylic acids, mono- or polyunsaturated C2 to C30 mono- or dicarboxylic acids, aromatic C5 to C30 mono- and dicarboxylic acids or a mixture of such carboxylic acids.

15. A lubricant composition according to claim 14, characterized in that the C2 to C30 monocarboxylic acids are selected from the group consisting of saturated monocarboxylic acids or monounsaturated monocarboxylic acids.

16. A lubricant composition according to claim 14 or 15, characterized in that the C2 to C30 monocarboxylic acids are selected from the group consisting of myristic, myristic, palmitic, palmitic, margaric, margarine, stearic, stearic, eicosanoic, eicosanoic, palmitoleic, palmitoleic, oleic , Oleic acid derivatives, elaidic acid, elaidic acid derivatives, icosenoic acid, icosenoic acid derivatives, cetoleic acid, cetoleic acid derivatives or mixtures thereof.

17. A lubricant composition according to claim 15 or 16, characterized in that the relative proportion

The trialkanolamine 5 to 25% by weight, preferably 10 to 20% by weight, The modified cellulose ether 0.5 to 5 wt.%, Preferably 1 to 3 wt.

%

The monocarboxylic acid is from 10 to 40% by weight, preferably from 20 to 35% by weight, of the total composition.

18. A lubricant composition according to claim 15 or 16, characterized in that the relative proportion of the trialkanolamine 1 to 15 wt .-%, preferably 5 to 10 wt .-%,

The modified cellulose ether 0.1 to 5 wt.%, Preferably 0.5 to 2 wt.

%

The monocarboxylic acid is from 1 to 10% by weight, preferably from 4 to 8% by weight, of the total composition.

19. Lubricant composition according to one of the preceding claims, characterized in that it contains an antifreeze, preferably selected from the group consisting of polyhydric alcohols, salts and ionic liquids.

A lubricant composition according to claim 19, characterized in that the polyhydric alcohol is glycerin.

21. Lubricant composition according to one of the preceding claims 19 or 20, characterized in that the antifreeze in a relative proportion of at most 60 wt .-%, preferably at most 30 wt .-%, particularly preferably of at most 15 wt .-%, in particular of at most 10% by weight is contained in the lubricant composition.

22. Lubricant composition according to one of the preceding claims, characterized in that it contains a corrosion inhibitor, preferably selected from the group consisting of triazoles, thiadiazoles, amine and alkali salts of sulfonates, phosphonates, thiophosphonates, carboxylic acids or mixtures thereof.

23. Lubricant composition according to one of the preceding claims, characterized in that it contains an emulsifier, preferably selected from the group consisting of organophosphates, fatty acid glycol ethers, Alkylpolyglykolethercarbonsäuren or mixtures thereof.

24. Lubricant composition according to one of the preceding claims 19 to 23, characterized in that the relative proportion of the trialkanolamine 5 to 25 wt .-%, preferably 10 to 20 wt .-%,

The modified cellulose ether 0.5 to 5 wt.%, Preferably 1 to 3 wt.

%

The monocarboxylic acid 10 to 40 wt .-%, preferably 20 to 35 wt .-%,

The polyethylene glycol is less than 5% by weight, preferably 0.01 to 0.1% by weight, of the metal hydroxide 0.5 to 5.0% by weight, preferably 1 to 3% by weight,

The corrosion inhibitor 0.5 to 5% by weight, preferably 1 to 3% by weight,

The antifreeze 3 to 20% by weight, preferably 5 to 15% by weight,

The emulsifier is from 1 to 5% by weight, preferably from 2 to 4% by weight, of the total composition.

25. A lubricant composition comprising water and a first component of one or more thickeners or salts thereof (thickener component) and a second component of one or more natural or chemically modified polymers or salts thereof (polymer component), characterized in that the thickener is the reaction product one or more diisocyanates, with an amine of the general formula R ' ₂ NR and / or a diamine of the general formula R' ₂ NRN-R ' ₂ , wherein R is an aryl, alkyl, or Allkylenrest, in particular a polyaryl, polyalkyl or a polyalkylene radical, or with a mixture of amines or diamines.

26. A lubricant composition according to any one of the preceding claims, characterized in that the electrical conductivity is in the range between 10 ^"12 and 10 ^" ³ S / cm.

27. Base oil for the preparation of a lubricant composition, characterized in that it contains water and a polymer component defined according to one of claims 1 to 26, preferably consists thereof.

28. Use of a composition defined according to any one of claims 1 to 26 or the base oil defined according to claim 27 for the preparation of a lubricant composition.

29. A process for preparing a lubricant composition comprising the following steps:

(iia) contacting the base oil with at least one thickener

(iii) optionally heating the mixture

(iv) optionally adding additives.

30. A process for preparing a grease composition according to claim 30, comprising the following steps:

(iii) optionally heating the mixture;

(iv) optionally adding additives.