KR20120139730A - Lubricating greases containing lignosulfonate, the production thereof, and the use thereof - Google Patents

Abstract

The present invention comprises a calcium lignosulfonate having an average molecular weight (weight average) of more than 10000 g / mol, together with a lubricating base oil, a calcium soap group, and optionally an alkaline earth lignosulfonate, to prepare a base grease. To this end, lubricating greases containing calcium lignosulfonate which can be prepared by heating to above 120 ° C., removing low boiling point components, cooling and adding lubricating base oils and optionally other additives, and the The present invention relates to a process for producing and lubricating grease containing calcium lignosulfonate.

Description

Lubricating grease containing lignosulfonate, production and use of the lubricating grease {LUBRICATING GREASES CONTAINING LIGNOSULFONATE, THE PRODUCTION THEREOF, AND THE USE THEREOF}

The present invention relates to a process for the preparation of calcium lignosulfonate and lubricating greases containing this kind and the use of such lubricating greases.

Lignin is a complex polymer of the phenylpropane unit family, and the phenylpropane unit is cross-linked with each other with the bandwidths of different chemical compounds. The lignin is present in plant cells along with cellulose and hemicellulose. The lignin itself is a crosslinked polymer having an average molecular weight, for example 10000 g / mol (weight).

As the monomer component of the ligno, three kinds of mono ligno-monomers which generally differ from each other in the degree of methoxylation can be identified. This is p -coumariyl alcohol, coniferyl alcohol, cinafil alcohol. These lignols are inserted into the ligno structure in the form of hydroxyphenyl (H)-, guaiacyl (G)-and inhaler (S) -units. For example, plants belonging to Naza plants (pine seeds), such as pine trees, mostly contain G-units, and contain low proportions of H-units. All lignos contain a low proportion of incomplete or modified mono lignols. The primary function of ligno in plants is to impart mechanical stability to these lignos through crosslinking of plant polysaccharides. Ligno represents approximately one third of the dry mass of wood and approximately 30% of the mass of non-fossil organic carbon on the ground. This is the third most used organic material after cellulose and chitin and together with it is also a renewable raw material that can be used for industrial products.

Lignosulfonate is obtained as a byproduct when making paper by the sulfurous acid method. It is also heated to a pressure of about 7 to 15 hours (for example 5 to 7 bar) in the presence of calcium hydrogensulfite liqueur for wood chips of pulverized wood, followed by a washing process and precipitation Through the process, the lignosulfonate is removed from the lignocellulose in the form of calcium lignosulfonate. In addition, magnesium liqueur, sodium liqueur or ammonium sulfide liqueur may be used instead of calcium hydrogen sulfite, which corresponds to the magnesium salt sodium salt and ammonium salt of lignosulfonate.

Due to the evaporation of the wash liqueur the lignosulfonate in powder form is obtained. Each year, worldwide production of lignosulfonates amounts to approximately 55 million tons.

Sodium sulfonate, calcium sulfonate and magnesium sulfonate are often used as basic raw materials for the plasticization and liquefaction of concrete and mortar. In addition, lignosulfonate is used as a dispersing or complexing agent in pelleting aids and other areas in the concentrate feed industry.

Extreme pressure (high pressure) and abrasion resistant additives (EP / AW-Additive), which act as tribo chemicals used in lubrication grease formulations today, represent a modest proportion of high formulation costs, often lubricant greases. Will be the price increase factor.

Many of these additives are manufactured in an expensive, multistage synthetic mode, and the use of additives is limited in the final formulation, not only in the mode of application, but also in the concentration of use, due to the frequent toxic side effects. For some applications, poor lubrication or friction partner contact due to liquid additives may be inevitable, for example in the case of constant velocity joints or slow driven, high load roll bearings. In this case, in the past practice, solid lubricants of inorganic compounds (e.g. calcium sulfonate and zinc sulfonate), plastic powder (e.g. PTFE) or metal sulfide (e.g. M _O S ₂ ) series Was used. However, these components are expensive and have a decisive influence on the overall cost of the lubricant formulation.

In the practice so far in the manufacture of lubricating greases, the addition of such additives has been carried out in the second, originally concentrated, subsequent process step of the chemical reaction. In this case, additives, in particular solid lubricants, must be evenly dispersed into relatively high viscosity lubricating greases through intensive mixing and shearing processes with high mechanical costs in order to achieve optimum effects. In today's view, this is often regarded as a disadvantage and gives the opportunity for the present application.

Commonly used lubricating additives and solid lubricants are usually not based on renewable raw materials and are often poorly biodegradable. In addition, most commonly used antiwear additives and friction reducing lubricating additives require costly chemical synthesis, which is a high cost factor. Especially when using solid lubricants for high load friction positions M _O S ₂ Or relatively expensive materials such as PEFE are used.

It is an object of the present invention to overcome the disadvantages of the prior art described above and to use lignosulfonate in lubricating greases as low cost structure forming agents and as antiwear, friction reducing and anti aging additives. And at the same time, to impart excellent water resistance to the lubricating grease.

By providing such lignosulfonate salts, the use of other lubricating additives and solid lubricants in common use, in particular M _O S ₂ , can be reduced or eliminated completely.

The invention is defined by the independent claims. Preferred embodiments are described in the dependent claims or described below.

According to the method of the invention, a first step (base grease) is first made by mixing at least the following:

-Base oil

Fatty acids and / or esters of said fatty acids or salts of said fatty acids, wherein said fatty acid salts are at least partly calcium salts and comprise at least calcium soap groups for producing soap groups,

Organic and / or inorganic complexing agents, if necessary,

Alkaline earth hydroxides, where alkaline earth hydroxides comprise at least CaOH,

Water, if necessary (eg as part of a hydroxide), and

Ca-lignosulfonate having an average molecular weight (weight average) of more than 10000 g / mol.

And lubrication if a complexing agent capable of reacting with alkaline earth hydroxides is used, in order to eliminate low boiling point components through heating and to cause the conversion of fatty acids and / or esters and lignosulfonates of the fatty acids and at least alkaline earth hydroxides. Reaction with complexing agents to form a concentrated structure of the base oil.

The low boiling point component is a boiling point component at about 100 ° C. at normal pressure, such as water or C 1 -alcohol to C 4 -alcohol.

Preferably, for the preparation of the base grease, the mixture is heated to a temperature above 120 ° C. or more preferably above 180 ° C. The conversion to the base grease is carried out in a heated reactor, which may be formed as an autoclave or a vacuum reactor.

In the next second step, the condensation structure formation is completed through cooling, and optionally other ingredients such as additives and / or lubricating base oils are added to adjust the desired concentration or desired property profile. The second stage can be carried out in the same reactor used in the first stage, but preferably the base grease is fed to a stirred tank reactor separated from the reactor for cooling and optionally mixing another component. Transferred.

If necessary, the lubricating grease thus obtained can be homogenized, filtered and / or bubbled.

Preferably, Ca / Li-, Li / Ca- and calcium-concentrated general soap greases and complex soap greases are used, in which case calcium lignosulfonate is added before the reaction step to prepare the base grease. It is provided in the form of a highly homogenized insoluble oil and integrated into the lubricating grease structure through heat treatment to achieve a high dropping point temperature.

For fatty acids and lignosulfonates, the use of alkaline earth salts, preferably calcium salts, ensures that salt metathesis does not occur not only in the preparation of the base grease but also in use.

In order to make lubricating greases containing lignosulfonic acid salts having good water resistance and at the same time a high dropping point, salt substitution with sodium salts in particular should be suppressed. Therefore, the use of sodium sulfonate and sodium hydroxide should be limited. Water resistance means that the grease is not emulsified due to water according to the test of DIN 51807-1 (version: 1979-04) or corresponds to evaluation level 1-90 (test temperature 90 ° C.). In addition, water resistance means that the grease corresponds to the evaluation level 1-80 (test temperature 80 ° C.) according to the test of DIN 51807-2 (version: 1990-03).

By simultaneously using excess alkali in the form of excess calcium hydroxide and optionally calcium acetate or another calcium salt as a complexing agent, a small residual of free sulfonic acid groups is neutralized in lignosulfonic acid salts, hygroscopic, water emulsifying and To ensure that it is free from corrosion promoting action. Through high process temperatures above 120 ° C., in particular above 180 ° C., further residual moisture remaining in the lignosulfonate is completely vaporized from the reaction medium, and in some cases the components of the unneutralized lignosulfonate are neutralized due to calcium hydroxide. Be sure to

Standard lubricants suitable for lubricating base oils are liquids at room temperature. This lubricating base oil preferably has a dynamic viscosity of 20 to 2500 mm ² / s, in particular 40 to 500 mm ² / s at 40 ° C.

The lubricating base oil may be classified as mineral oil or synthetic oil. As mineral oil, for example, naphthenic and paraffinic mineral oils according to the classification of API Group I can be considered. Chemically modified aromatic and sulfur-free mineral oils with improved viscosity- / temperature-appearance compared to small amounts of saturated compounds and Group I are also suitable and are classified according to API Group II and III. do.

As the synthetic oil, polyethers, esters, polyalphaolefins, polyglycols and alkyl aromatics and mixtures thereof may be considered. Polyether compounds include free hydroxyl groups, but may be fully etherified, or terminal groups may be esterified, and / or prepared from starter compounds having one or more hydroxyl groups and / or carboxyl groups (—COOH). If desired, the polyphenylether may also be considered as a single component or preferably a mixed component, whether alkylated or not. Dicarboxylic acid, tri-carboxylic acid or tetra-carboxylic acid, adipic acid, sebacic acid, trimethylolpropane, neopentylglycol, pentaerythritol or branched or branched suitably present in single or mixed form Aromatic dicarboxylic acids, tri-carboxylic acids or tetra-carboxes with dipentaerythritol having unsaturated or unsaturated aliphatic C2 to C22-carboxylic acids, C18-dimer esters with C2 to C22-alcohols Esters of acids can be used in single component or in optional mixtures.

The soap groups produced are pure calcium soap groups or mixtures containing calcium soap groups, in particular 10 to 32 carbons containing 12 to 22 carbon atoms which may be substituted with lithium soap groups and / or in particular with said calcium soap groups. Mixtures comprising aluminum soap groups of single or multiple saturated or unsaturated monocarboxylic acids with atoms, particularly preferably of the corresponding hydroxycarboxylic acids. Suitable carboxylic acids are, for example, lauric acid, myristic acid, palmitic acid, oleic acid, stearic acid or behenic acid and preferably 12-hydroxystearic acid. Instead of the free acid group the corresponding low alcohol esters can also be used under soap groups to achieve improved dispersion, for example the corresponding triglycerides and methyl-, ethyl-, propyl-, isopropyl- Or secondary butyl esters may be used.

Soap groups turn into complex soaps due to the presence of complexing agents . The complex soaps (in the presence of complexing agents ) according to the invention have a high dropping point, for example above 200 ° C. (DIN ISO 2176). Preferably, from 0.5 to 20% by weight, in particular from 0.5 to 10% by weight of complexing agents are used.

For the purposes of the present invention, the following complexing agents are preferred:

(a) alkali salts (preferably lithium salts), alkaline earth salts (preferably calcium salts) or saturated or unsaturated monocarboxylic acids or, if necessary, substituted 2 to 8, in particular 2 to 4, except for sodium salts Hydroxycarboxylic acids having carbon atoms of or dicarboxylic acids having 2 to 16, especially 2 to 12, carbon atoms, and / or

(b) reactants with alkali and / or alkaline earth salts of boric acid and / or phosphoric acid, in particular LiOH and / or Ca (OH) ₂ .

Preferably, the complexing agent (a) is only a calcium salt, especially when used as calcium acetate for preparing base grease. In particular, acetic acid and propionic acid are suitable as monocarboxylic acids. Similarly, hydroxybenzoic acid is also suitable, for example, paraoxybenzoic acid, salicylic acid, 2-hydroxy-4-hexylbenzoic acid, metahydroxybenzoic acid, 2,5-dihydroxybenzoic acid (gentisic acid), 2,6-dihydrate Hydroxybenzoic acid (Gammarresorcylsaeure) or 4-hydroxy-4-methoxybenzoic acid. Particularly suitable as dicarboxylic acids are adipic acid (C ₆ H ₁₀ O ₄ ), sebacic acid (C ₁₀ H ₁₈ O ₄ ), azelaic acid (C ₉ H ₁₆ O ₄ ) and / or 3-tert-butyl- Adipic acid (C ₁₀ H ₁₈ O ₄ ).

As borate (b), for example, orthoborate such as metaborate, diborate, triborate or monolithium orthoborate or calcium orthoborate can be used. As phosphates, alkali (preferably lithium-) dihydrogen phosphates and alkaline earth salts (preferably calcium-) dihydrogen phosphates, -hydrogen phosphates, or -pyrophosphates can be used.

Optionally, montmorillonite (sodium-ion of montmorillonite is optionally or partially replaced with ammonium-ion), aluminum silicates, clays, silicic acids (eg aerosil), oil-soluble polymers (eg , Polyolefins, poly (meth) acrylates, polyisobutylene, polybutene or PS) or bentonites such as di-urea and polyurea may further be used as co-thickeners. Bentonite, aluminum silicates, clays, silicic acids and / or oil soluble polymers may be added for base grease preparation, or may later be injected as additives in a second step. Di-urea and polyurea may be injected as additives.

The compounds according to the invention may also comprise other additives as adducts, if necessary. Additional elements for the purposes of the present invention are antioxidants, antiwear agents, corrosion inhibitors, detergents, colorants, lubrication improvers, viscosity additives, friction reducers, and high pressure additives.

E.g:

Antioxidants are for example amine-compounds (eg alkylamines or 1-phenyl-aminonaphthalene), for example aromatic amines such as phenylnaphthylamine or diphenylamine, phenol-compounds (eg 2.6- Di-tert-butyl-4-methylphenol), sulfur antioxidant, zincdithiocarbamate or zincdithiophosphate;

High pressure additives are organochlorine compounds, sulfur, phosphorus or calcium borate, zinc dithiophosphate, organobismuth compounds;

Substances which enhance "oiliness" are, for example, C2- to C6-polyols, fatty acids, fatty acid esters or animal or vegetable oils;

Corrosion inhibitors are for example petroleum sulfonates, dinonylnaphthalenesulfonates or sorbitan esters;

Metal particle removers are, for example, benzotriazole or sodium nitrite;

Viscosity improving agents are for example polymethacrylates, polyisobutylenes, oligo-Dec-1-enes and polystyrenes;

Anti-wear additives and friction reducing agents such as organic molybdenum composites (OMC), molybdenum-di-alkyl-dithiophosphates, molybdenum-di-alkyl-dithiocarbamates or molybdenum sulfide-di-alkyl-dithiocarbames Acid salts, especially molybdenum-di-n-butyldithiocarbamate and molybdenum disulfide-di-alkyldithiocarbamate (Mo ₂ OmSn (dialkylcarbamate) ₂ m = 0 to 3 and n = 4 to There is 1);

Friction reducing agents are for example functional polymers, for example oleylamides, for example polyether-based and amide-based organic compounds such as alkylpolyethyleneglycoltetradecylene glycolethers.

In addition, the lubricating grease compounds according to the invention also comprise general additives for protection against corrosion, oxidation and the effects of metals acting as chelating compounds, radacal scavengers, UV-converters, reaction layer formers and the like. do.

As solid lubricants , for example powdered polymers can be used, for example polyamide, polyimide or PEFE, graphite, metal oxides, boron nitride and metal sulfides such as molybdenum disulfide, tungsten disulfide or tungsten, molybdenum Mixed sulfides of the bismuth, tin and zinc series, for example inorganic salts of alkali metals and alkaline earth metals such as calcium carbonate, sodium phosphate and calcium phosphate. The solid lubricants can be classified into four groups as follows: compounds having a layered lattice structure such as molybdenum disulfide and tungsten disulfide, graphite, hexagonal boron nitride and some metal halides; Oxidative and hydroxy compounds of transition metals and alkaline earth metals or carbonates or phosphates of said metals; Soft metals and / or plastics. Desired desired lubricating properties can be adjusted by using lignosulfonates without the use of solid lubricants. Most solid lubricants can be completely removed or at least significantly reduced. If a solid lubricant is used, graphite is most preferred.

Lignoceric sulfonic acid salt as a 10,000 g / mol in excess, in particular 12000 g / mol greater than or 15,000 g / mol greater than, for example, 10000 to 65000 g / mol or 15 000 to 65000 g / with the mol molecular weight (Mw, weight average) Calcium-lignosulfonic acid salts may be selected, wherein the calcium-lignosulfonic acid salts are in particular from 2 to 12% by weight, particularly preferably from 4 to 15% by weight of sulfur (calculated as elemental sulfur) and / or from 5 to 15% by weight, in particular 8-15% by weight of calcium (calculated as Ca). In addition, calcium-lignosulfonate salts, other alkaline earth lignosulfonate salts may also be used. Average molar weights (weight averages) are measured, for example, by Size Exclusion Chromatography. A suitable method is the SEC-MALLS method, described in GE Fredheim, SM Braaten and BE Christensen, in the article "Comparison of molecular weight and molecular weight distribution of softwood and hardwood lignosulfonates", which is "Journal of Wood Chemistry and Technology". , Vol. 23, Nr. 2, pages 197-215, 2003. The method is also known from the same author's article "Molecular weight determination of lignosulfonates by size exclusion chromatography and multi-angle laser scattering", which is published in Journal of Chromatography A, Volume 942, 1st-2nd edition, 4 January 2002, 191-199 (mobile phase: phosphate-DMSO-SDS, fixed phase: Jordi-glucose-DVB and 2.5 known below). Suitable calcium lignosulfonates are, for example, products of the commercially available Norlig 11D and Borrement Ca 120 from Borregard Lignotech.

The lubricating greases according to the invention are each characterized by having the following composition for the whole compound:

a) lubricating base oil, 55 to 92% by weight, in particular 70 to 85% by weight,

b) additive, 0 to 40% by weight, in particular 2 to 10% by weight,

c) soap groups, 3 to 40% by weight, in particular 5 to 20% by weight,

d) complexing agents, 0 to 20% by weight or 0.5 to 20% by weight, in particular 0.5 to 10% by weight,

e) excess Ca (OH) ₂ , preferably 0.01 to 2% by weight,

f) lignosulfonates, in particular calcium lignosulfonates, 0.5 to 50, in particular 2 to 15% by weight and particularly preferably 3 to 8% by weight.

The components and preferred variants thereof are as described above.

It has been found that the lignosulfonate acts as structure forming agents for water resistant lubricating greases which also have properties as solid lubricants or antiwear additives and as aging stabilizers. At the same time, it has been observed that lignosulfonate has a surprising synergistic effect with other solid lubricants, for example graphite or calcium carbonate.

It has also been found that the lignosulfonate salt is a multi functional ingredient as a lubricant. Due to the large polar group quantity and aromatic structure, it has low solubility in its polymer structure and all kinds of lubricants, and therefore the lignosulfonate is suitable for use as a solid lubricant in lubricating greases and lubricating pastes as well as as a concentrator component. . In addition, the sulfur content promotes EP-AW-action in lubricating grease, and the phenolic structure provides anti-aging action.

The lignosulfonate structure is assumed to have a very flat structure due to the polymer and polar aromatic units present in large quantities.

Thus, the lignosulfonate structure can be deposited very well on the metal surface in a layered structure under the influence of external frictional and shear forces, because the aromatic nuclei of the lignosulfonate interact with the metal surface and also At high loads or pressures, metal friction partners are effectively and continually separated from each other.

When calcium-lignosulfonate is added before the reaction step when preparing soap-based thickeners, in particular calcium complex soaps, on the one hand, the calcium-lignosulfonate affects further thickening effects and high dropping point, on the other hand This improves the wear protection and lubrication effect of the corresponding lubricating grease. Thus, when the calcium-lignosulfonate is chemically or mechanically linked to a thickener structure present as an additional structural element during the reaction step, it may be useful for the distribution and action of additives and solid lubricants.

In order to prepare soap-based greases with a high dropping point, the prior art often requires specially treated expensive fatty acids, for example of 12-hydroxystearic acid or of borate or acetic acid, sebacic acid and azelaic acid. Special complexing agents such as salts fall into this category and the fatty acids do not have any effect as antiwear additives and friction reducing additives or have only minor effects. The use of the calcium-lignosulfonate salts can be reduced or the use of the above components can be avoided. In addition, the use of the calcium-lignosulfonate offers the possibility of formulating high performance lubricating greases based on recycled raw materials and avoiding chemical additives that are harmful to the environment.

When thickening oils consisting of unmodified or slightly modified natural fatty acid esters with animal or vegetable fatty acid soaps and using the lignosulfonate as the only another thickener component and simultaneous additive component, Lubricating greases prepared on the basis of only recycled raw materials except for the calcium hydroxide used for this purpose are obtained. The use of lignosulfonates as thickener ingredients provides anti-aging, anti-wear and increased seizure loads and reduced friction.

The lubricating grease according to the invention can be used particularly suitably for use in the constant velocity joints, roll bearings and gearboxes or for the aforementioned.

If the lubricating base oil used is composed of good biodegradable esters such as, for example, renewable raw materials, lubricating greases are suitably used even if the lubricant leaks in environmentally sensitive areas (eg mining or agriculture).

In the special case of lubricating a constant velocity joint that requires no maintenance, lubricating grease is first formulated using calcium lignosulfonate, which, in contrast to the prior art, has a long overall life without MoS ₂ and other organic and inorganic molybdenum compounds. And excellent efficiency.

In addition, avoiding the use of other additives for coefficient of friction, fixed load protection and friction protection results in very good compatibility with commercially available constant velocity joint bellow materials such as chloroprene rubber and thermoplastic polyetheresters. Since sulfur contained in the lignosulfonate is linked to a thermally stable sulfonic acid group, the sulfur is released in the case of high active energy, such as occurs only in the case of very high temperature or frictional contact under high load when using lubricating grease. Can be. As a result, subsequent vulcanisation or crosslinking of the rubber material is continuously suppressed through the sulfur released from the aged lubricant.

The use of calcium lignosulfonate in lubricating grease formulations adjusted to excess basic due to excessive calcium hydroxide inhibits the free lignosulfonate from causing hydrolysis to the bellows ash and to the thermoplastic polyetherester.

A particular aspect of the present invention is to achieve a lubricating grease formulation at an optimum cost, especially for high loaded lubrication points, such as in constant velocity joints, which are for example thermoplastic polyetherester (TPE) and chloroprene (CR). High efficiency, low wear and long service life while providing excellent compatibility for bellows configuration.

Manufacturing example

Example A ( Comparative example ):

958 g of resin fatty acid, 958 g of tallow, 958 g of calcium acetate, 27.7 g of trisodium phosphate, 27.7 g of calcium borate and 358 g of calcium hydroxide were provided to a reactor of a 12000 g lubricating base oil mixture, and 150 ml of water was added. The base was heated with stirring to 198 ° C. under a defined temperature program, at which time the added water and reactants were vaporized. Additives (see table) were added to the base at specific temperatures during the cooling step. After adjusting the base to the desired consistency through the addition of 3700 g of base oil mixture, the final product was homogenized through a toothed colloid mill. The grease thus obtained is suitable, for example, as a constant velocity joint grease.

Example B:

460 g of resin fatty acid, 445 g of tallow, 460 g of calcium acetate, 27.7 g of trisodium phosphate, 27.7 g of calcium borate, and 168 g of calcium hydroxide and 920 g of calcium lignosulfonate (Borregard Lignotech powder Norlig 11D) were provided in a reactor of 14000 g of a lubricating base oil mixture. , 150 ml of water was added. The base was heated with stirring to 208 ° C. in a defined temperature program, at which time the added water and reactants were vaporized. Additives (see table) were added to the base at specific temperatures during the cooling step. After adjusting the base to the desired consistency through the addition of 3450 g of base oil mixture the final product was homogenized through a toothed colloid mill. The grease thus obtained is suitable, for example, as a constant velocity joint grease.

Example C ( Comparative example ):

800 g of 12-hydroxystearic acid, 288 g of sebacic acid, 388 g of calcium acetate, 157.3 g of calcium hydroxide were prepared in a reactor of 5000 g of a lubricating base oil mixture. 64 g of LiOH x H ₂ O were dissolved and added in 250 ml of water. The base was heated with stirring to 200 ° C. in a defined temperature program, at which time the added water and reactants were vaporized. Additives were added to the base at specific temperatures during the cooling step.

After adjusting the base to the desired consistency through the addition of 3116 g of base oil mixture the final product was homogenized through a toothed colloid mill. The grease thus obtained is suitable, for example, as grease for roll bearings.

Example D:

600 g of 12-hydroxystearic acid, 216 g of sebacic acid, 291 g of calcium acetate, 720 g of calcium hydroxide and 300 g of calcium lignosulfonate (powder Norlig 11D from Borregard Lignotech) were prepared in a reactor of 5000 g of a lubricating base oil mixture. 48 g of LiOH x H ₂ O was dissolved and added in 250 ml of water. The base was heated with stirring to 200 ° C. in a defined temperature program, at which time the added water and reactants were vaporized. Additives were added to the base at specific temperatures during the cooling step. After adjusting the base to the desired consistency through the addition of 3116 g of base oil mixture, the final product was homogenized through a toothed colloid mill. The grease thus obtained is suitable, for example, as grease for roll bearings.

Example E ( Comparative example ):

1380 g of resin fatty acid, 1360 g of tallow, 80 g of trisodium phosphate, 80 g of calcium borate, 1400 g of calcium acetate, and 493 g of calcium hydroxide were provided to a reactor of a 12000 g lubricating base oil mixture, and 150 ml of water was added. The base was heated with stirring to 230 ° C. in a defined temperature program, at which time the added water and reactants were vaporized. Additives were added to the base at certain temperatures during the cooling step. After adjusting the base to the desired consistency through the addition of 3125 g of base oil mixture, the final product was homogenized through a toothed colloid mill. The grease thus obtained is suitable, for example, as a constant velocity joint grease.

Example F:

1260 g of resin fatty acid, 1240 g of tallow, 1,200 g of trisodium phosphate, 80 g of calcium borate, 1270 g of calcium acetate and 493 g of calcium hydroxide and 885 g of calcium lignosulfonate (Borregard Lignotech powder Norlig 11D) were provided in a reactor of 12000 g of lubricating base oil mixture, 150 ml was added. The base was heated with stirring to 225 ° C. in a defined temperature program, at which time the added water and reactants were vaporized. Additives were added to the base at certain temperatures during the cooling step. After adjusting the base to the desired consistency through the addition of 3125 g of base oil mixture, the final product was homogenized through a toothed colloid mill. The grease thus obtained is suitable, for example, as a constant velocity joint grease.

Example G ( Comparative example ):

975 g of calcium-12-hydroxystearate, 225 g of calcium acetate and 15 g of calcium borate were provided in a reactor of 3500 g of methyl calcium oleic acid-ester. The base was heated with stirring to 200 ° C. in a defined temperature program. Additives were added to the base at a predetermined temperature during the cooling step. After adjusting the base to the desired consistency through the addition of 180 g of methyl calcium oleic acid-ester, the final product was homogenized through a 3-roller mill. The lubricating grease thus obtained consists mostly of recycled raw materials.

Example H:

841 g of calcium-12-hydroxystearate, 219.5 g of calcium acetate and 15 g of calcium borate and 418 g of calcium ignosulfonate (powder Norlig 11D from Borregard Lignotech) were provided in a reactor of 1965 g of methyl calcium oleic acid-ester. The base was heated with stirring to 200 ° C. in a defined temperature program. Additives were added to the base at a predetermined temperature during the cooling step. After adjusting the base to the desired consistency through the addition of 1684 g of trimethylolpropanetrioleate, the final product was homogenized through a three-roller mill. The lubricating grease thus obtained consists mostly of recycled raw materials.

Example I and J:

Embodiments I and J correspond to the preparation of Example H using calcium-12-hydroxystearate, different amounts of calcium acetate and calcium lignosulfonate, and different compounds of ester-lubricating base oils. The lubricating grease thus obtained consists mostly of recycled raw materials.

 Joint Shaft Grease-Formed Yes A B compare Invention Contents Calcium Complexes with MoS ₂ Calcium complex with 6% lignosulfonate Thickener 1.1 Lignosulfonate Calcium Lignosulfonate 0.0 6.1 1.2 Fatty Acids / -Triglycerides: Mixed Fatty Acids 4.8 2.9 Mixed Triglycerides 4.8 2.8 1.3 alkali hydroxy Ca (OH) 2 1.8 1.5 1.4 Complexing Agent Calcium acetate 4.8 3.0 Calcium borate 0.1 0.2 2. Lubrication base oil Mixed Basic Mineral Oils
(v40 = 100mm ² / s) 79.5 80.8 3. Additive Antioxidants 1 0.6 0.5 Antioxidant 2 0.6 0.5 Corrosion inhibitor 0.5 0.2 Solid lubricant graphite 0.5 1.0 Solid lubricant MoS2 1.8 0.0 sum 100 100 4. Characteristics Way unit 4. 1 General Physical Data Unmixed led
(Penetration unworked) DIN ISO 2137 0.1 mm 263 315 Mixed led 60 double cycle
(Penetration worked 60 double cycles) DIN ISO 2137 0.1 mm  351 340 Copper corrosion 24h / 100 ℃ DIN 51811 Evaluation level 1-100 1-100 Drop Point DIN ISO 2176 ℃ 240 280 Oily Water Separation 18h / 40 ℃ DIN 51817 % 0.4 2.1 Oil-water separation 7d / 40 ℃ DIN 51817 % 2 8.9 4.2 Water resistance Static water resistance 3h / 90 ℃ DIN 51807-1 Evaluation level 1-90 1-90 Loss of Wash Removal at 80 ° C DIN 51807-2 Evaluation level One One 4.3 Friction Reduction SRV at 80 ° C (40 Hz, 1.5 mm amplitude, 500 N load) ASTM D D5707-05 Coefficient of friction 0.107 0.097 Progress stability stability SRV at 150 ° C (40 Hz, 1.5 mm amplitude, 500 N load) ASTM D D5707-05 Coefficient of friction 0.907 0.085 Progress stability stability 4.4. Anti-wear effect VKA-Welding Load DIN 51350-4 N 3400 3800N VKA-Carlott 1000N / 1min DIN 51350-5 mm 1.02 0.62 4.5 Compatibility with Bellows Materials 4.6.1 Chloroprene Inepsa 4012 168h / 120 ℃ Shore A DIN 53505 -2 -One -Volume change DIN 53521 % +3.5 -0.5 -Tension change DIN 53504 % -0.5 -1.2 -Elongation change DIN 53504 % -22.1 -19 4.6.2 NBR-Rubber SRE NBR 34 7d / 100 ℃ Shore A DIN 53538-3 -2 -3 -Volume change DIN 53505 % +3.4 +3.1 -Tension change DIN 53521 % -2.9 -5 -Elongation change DIN 53504 % -7.8 -4.5 4.6.3 TPE-elastic polymer DIN 53504 Hytrel 8332 336h / 125 ℃ Shore D DIN 53505 -3 -2 -Volume change DIN 53521 % +13.1 +6.2 -Tension change DIN 53504 % -32.9 +6.7 -Elongation change DIN 53504 % -27 +61 Arnitel EB 463 336h / 125 ℃ Shore D DIN 53505 -6 0 -Volume change DIN 53521 % +10.7 +10.2 -Tension change DIN 53504 % -15 -19.7 -Elongation change DIN 53504 % -10 +7.8 4.6.4 EPDM-Rubber Vamac Y76HR 336h / 125 ℃ +3 +5 Shore A DIN 53505 +6 +0.3 -Volume change DIN 53521 % -17.4 -1.8 -Tension change DIN 53504 % -39 -35 -Elongation change DIN 53504 % 5. Constant velocity joint shaft life inspection life span Mio Over Rolling 13.6 11.2 Medium steady-state temperature ℃ 41.1 38.8

Roll Bearing Grease-Forming Yes C D E F compare Invention compare Invention Contents Calcium / Lithium Complex Calcium / lithium complex with 6% lignosulfonate Calcium complex Calcium / lithium complex with 5% lignosulfonate Thickener 1.1 Lignosulfonate Calcium Lignosulfonate 0.0 6.0 0 5.1 1.2 Fatty Acids / Triglycerides: 12-HSA 8.0 5.0 Mixed Fatty Acids 6.9 5.6 Mixed Triglycerides 6.8 5.4 1.3 Alkali hydroxy: LiOH * H2O 0.6 0.4 Ca (OH) 2 1.6 1.0 2.5 2.0 1.4 Complexing Agents: Sebas 2.9 1.8 Calcium acetate 3.9 2.4 7.0 5.7 Calcium borate 0.4 0.3 2. Lubrication base oil Mixed basic mineral oil (v40 = 100mm ² / s) 81.6 82.0 75.6 75.3 3. Additive Antioxidants 1 0.2 0.2 0.2 0.2 Antioxidant 2 0.2 0.2 0.2 0.2 Corrosion inhibitor One One 0.4 0.3 sum 4. Features Way unit 4.1 General Physical Data Unmixed led DIN ISO 2137 0.1mm 299 278 199 196 Mixed led 60 double cycle DIN ISO 2137 0.1mm 310 299 234 242 Drop Point DIN ISO 2176 ℃ 206 230 255 > 260 Oily Water Separation 18h / 40 ℃ DIN 51817 % 2.2 1.1 0 0 Oil-water separation 7d / 40 ℃ DIN 51817 % 4.1 3.9 0.8 0.6 4.2 Water resistance Static water resistance 3h / 90 ℃ DIN 51807-1 Evaluation level 1-90 1-90 1-90 1-90 Loss of Wash Removal at 80 ° C DIN 51807-2 Evaluation level One One One One 4.3 Corrosion Protectors Emcor distilled water DIN 51802 Evaluation level 0-0 0-0 0-0 0-0 4.5 Wear protection effect VKA-welding load DIN 51350-4 N 2000 3400 200 3200 VKA-Carlott 1000N / 1min DIN 51350-5 0.1mm 0.91 0.45 0.89 0.67 5. Roll bearing test FAG-FE9 (A / 1500/6000/120 ℃) DIN 51821-2 Life expectancy L10 78 110 35 78 Medium life L50 115 220 74 156

Lubricant grease formulation with lubricating base oil composed of recycled raw materials Yes G H I J compare Invention Invention Invention Contents Calcium complex Calcium complex Calcium complex Calcium complex One. Thickener 1.1 Lignosulfonate Calcium Lignosulfonate 0 7.1 9.9 5.1 1.2 Soaps Made: Ca-12 hydroxy stearate 19.5 14.1 19.8 10.1 1.6 Complexing agent : Acetate and calcium 4.5 2.9 4.0 2.1 Calcium borate 0.3 0.2 0.3 0.1 2. Lubrication Base oil Trimethylolpropanetrioleic acid 28.5 Methyloleic acid 73.6 73.6 63.9 52.1 3. Additive Antioxidants 1 0.1 0.1 0.1 0.1 Corrosion inhibitor 2 2.0 2.0 2.0 sum 100 100 100 100 4. Characteristics Way unit 4.1 General Physical Data DIN ISO 2137 0.1mm 189 108 170 232 Unmixed led DIN ISO 2137 0.1mm 221 209 219 301 Mixed led 60 double cycle DIN 51811 Evaluation level 1-100 1-100 1-100 1-100 Copper corrosion 24h / 100 ℃ DIN ISO 2176 ℃ 210 250 248 205 Drop Point DIN 51817 % 0.4 0.0 0.0 0.4 Oily Water Separation 18h / 40 ℃ DIN 51817 % 0.6 0.5 0.1 2.5 Oil-water separation 7d / 40 ℃ 4.2 Water resistance Static water resistance 3h / 90 ℃ DIN 51807-1 Evaluation level 1-90 1-90 1-90 1-90 4.3 corrosion inhibitor Emcor distilled water DIN 51802 Evaluation level 1-1 1-1 1-1 1-1 4.5 Wear protection effect VKA-welding load DIN 51350-4 N 2000 2800 3000 2400 VKA-Carlott 1000N / 1mm DIN 51350-5 0.1mm 0.89 0.67 0.54 0.48

Claims (23)

A process for preparing lubricating grease containing lignosulfonate, comprising the following steps:
a) mixing at least the following,
-Lube base oils,
Calcium soap groups having at least 10 carbon atoms, wherein the calcium soap groups are in place ( in situ ) if prepared, at least calcium hydroxide is added,
Calcium lignosulfonates having an average molecular weight (weight average) greater than 10000 g / mol,
Heating to a temperature above 120 ° C. for reaction and removing low boiling point components for base grease preparation, and
b) cooling and adding lubricating base oil with additives if necessary. The method of claim 1,
In step a), calcium hydroxide is added with another alkaline earth hydroxide if necessary. The method of claim 1,
The lubricating grease is in particular alkaline controlled through the addition of excess calcium hydroxide. The method of claim 1,
The heating is carried out at a temperature higher than 180 ° C. The method of claim 1,
In the step a), together with the calcium hydroxide, lithium hydroxide, magnesium hydroxide and / or aluminum hydroxide and / or aluminum alcoholate and / or aluminum oxoalcoholate and / or substituted or unsubstituted 10 to 32 carbon atoms A lithium soap group, a magnesium soap group and / or an aluminum soap group of a saturated or unsaturated monocarboxylic acid are used. The method of claim 1,
For each of the total composition of the lubricating grease, the lubricating grease contains independently of each other:
55 to 92% by weight, in particular 70 to 85% by weight of lubricating base oil,
From 0 to 40% by weight, in particular from 2 to 10% by weight of additives,
3-40% by weight of soap groups, in particular 5-20% by weight,
0 to 20% by weight of complexing agent, in particular 0.5 to 10% by weight, and
Excess Ca (OH) ₂ if desired, preferably 0.01 to 2% by weight,
Calcium to lignosulfonate, from 0.5 to 50, in particular from 2 to 15% by weight, particularly preferably from 4 to 8% by weight, together with another alkaline earth lignosulfonate salt if necessary. The method of claim 1,
The base grease of step a) can be prepared using the following for the composition of the base grease, respectively:
40 to 70% by weight of lubricating base oil, in particular 45 to 60% by weight,
From 10 to 60% by weight, in particular from 15 to 50% by weight of soap groups,
From 0 to 30, in particular from 5 to 20% by weight of a complexing agent, and
Excess Ca (OH) ₂ if desired, preferably 0.02 to 4% by weight,
0.7-50, especially 4-30% by weight of calcium lignosulfonate, with another alkaline earth sulfonate if necessary. The method according to claim 1 or 4,
The lubricating greases, independently of one another, comprise from 0.2 to 5% by weight of graphite, and / or contain no solid lubricants or comprise <1% by weight of solid lubricants, in particular no MoS ₂ . Manufacturing method. The method of claim 1,
The calcium soap groups, in situ, as esters or anhydrides, if necessary, react with calcium hydroxide with saturated or unsaturated monocarboxylic acids having from 10 to 32 carbon atoms, in particular from 16 to 20 carbon atoms, for example substituted by hydroxy A product, which is produced as a product. The method of claim 1,
As esters or anhydrides, saturated or unsaturated monocarboxylic acids having 2 to 8, especially 2 to 4 carbon atoms, if necessary, for example, each substituted with hydroxy, or 2 to 16, especially 2 to 12 carbon atoms A complexing agent as a reaction product of dicarboxylic acid and calcium salt, in particular calcium hydroxide, having a compound added during step a). The method of claim 1,
The complexing agent is a calcium salt of carboxylic acid, and during step a), in situ, as esters or anhydrides, from 2 to 8, in particular 2 to 4 carbon atoms, if necessary, each substituted with hydroxy, for example A process characterized in that it is prepared through the addition of saturated or unsaturated monocarboxylic acids having or dicarboxylic acids having from 2 to 16, in particular from 2 to 12, carbon atoms. The method according to any one of claims 1 to 11,
Said calcium-lignosulfonic acid salt is dehydrated to less than 0.5% by weight of water prior to addition by heating said lubricating base oil to, for example, more than 95 ° C, in particular from 100 ° C to 120 ° C. The method according to at least one of claims 1 to 12,
The composition is characterized in that it comprises 0.5 to 20% by weight, in particular 0.5 to 10% by weight of a complexing agent. A lubricating grease compound, each comprising the following for the total composition of the lubricating grease:
55 to 92% by weight, in particular 70 to 85% by weight of lubricating base oil,
From 0 to 40% by weight, in particular from 2 to 10% by weight of additives,
3-40% by weight, in particular 5-20% by weight of calcium soap groups having 10 or more carbon atoms,
Excess Ca (OH) ₂ if desired, preferably 0.01 to 2% by weight,
Calcium to lignosulfonate of 0.5 to 50% by weight, in particular 2 to 15% by weight and particularly preferably 2 to 8% by weight, together with another alkaline earth lignosulfonate salt if necessary. 15. The method of claim 14,
The compound has a cone penetration value (worked penetration) of 265 to 385 mm / 10 (at 25 ° C.), preferably 285 to 355 mm / 10, defined according to ISO 2137. Characterized by a compound. The method according to any one of claims 14 or 15,
The lubricating base oil has a kinematic viscosity of 20 to 2500 mm ² / s, preferably 40 to 500 mm ² / s at 40 ° C. The method according to any one of claims 14 to 16,
The complexing agent,
Alkali salts, preferably lithium salts, alkaline earth salts, preferably calcium salts or saturated or unsaturated monocarboxylic acids having 2 to 8, in particular 2 to 4 carbon atoms, each substituted if necessary, or 2 Compounds characterized in that they consist of dicarboxylic acids having from 16 to 16, in particular from 2 to 12, carbon atoms. The method according to any one of claims 14 to 17,
Wherein said additive comprises one or more elements selected from the following groups:
Antioxidants such as amine-compounds, phenol-compounds, sulfur antioxidants, zincdithiocarbamate or zincdithiophosphate;
High pressure additives such as organochlorine compounds, sulfur, phosphorus or calcium borate, zinc dithiophosphate, organobismuth compounds;
C2- to C6-polyols, fatty acids, fatty acid esters or animal or vegetable oils;
Corrosion inhibitors such as petroleum sulfonate, dinonylnaphthalenesulfonate or sorbitan esters;
Metal particle removers such as benzotriazole or sodium nitrite;
Viscosity improvers such as polymethacrylate, polyisobutylene, oligo-Dec-1-ene and polystyrene;
Antiwear additives such as molybdenum-di-alkyl-dithiocarbamate or molybdenum sulfide-di-alkyl-dithiocarbamate, aromatic amines;
Functional polymers, for example oleylamides, polyether-based and amide-based organic compounds, friction reducing agents such as molybdenum dithiocarbamate (friction reducing agents);
Powdered polymers, for example polyamide, polyimide or PEFE, graphite, metal oxides, boron nitride, for example molybdenum disulfide, tungsten disulfide, or mixed sulfides of tungsten, molybdenum, bismuth, tin and zinc series Solid lubricants, such as inorganic salts of metal sulfides, for example alkali metals and alkaline earth metals such as calcium carbonate, sodium phosphate and calcium phosphate. The method according to any one of claims 14 to 18,
The lubricating grease, in particular,
Corresponding to evaluation level 1-90 according to the test of DIN 51807-1, and / or
A compound having a water resistance, corresponding to the evaluation level 1-80 according to the test of DIN 51807-2. The method according to any one of claims 14 to 19,
The calcium-lignosulfonate has an average molecular weight (Mw, weight average) of more than 10000 g / mol, in particular of 12000 g / mol or of more than 15000 g / mol, independently 2 to 12% by weight, in particular 4 to 15% by weight. % Sulfur (calculated as elemental sulfur), and / or independently 5 to 15% by weight, in particular 8 to 15% by weight of calcium (calculated as Ca). The method according to any one of claims 14 to 20,
Wherein the lubricating grease comprises a lubricating base oil of the regeneration raw material series, and / or at least 95% by weight of the lubricating base oil is prepared based on the regeneration raw material. The method according to any one of claims 14 to 21,
The compound is characterized in that it comprises 0.5 to 20% by weight, in particular 0.5 to 10% by weight of a complexing agent. Use of a compound according to at least one of claims 14 to 22 for lubricating at least constant velocity joints, in particular parts of constant velocity joint shafts, transmissions and roll bearings and friction bearings.