MX2012008960A - Lubricating greases containing lignosulfonate, the production thereof, and the use thereof. - Google Patents

Abstract

The invention relates to lubricating greases that contain calcium lignosulfonate, comprising a base oil, calcium soaps, calcium lignosulfonate having average molecular weights (weight average) of greater than 10000 g/mol, optionally in addition to further alkaline earth lingosulfonates, which can be produced by heating to greater than 120 °C while reacting and while driving out low-boiling components to produce a basic grease and cooling and adding base oil and optionally additives while mixing, to a corresponding method, and to the use of the lubricating greases containing calcium lignosulfonate.

Description

LUBRICATION GREASES CONTAINING LIGNIN SULFONATE, PRODUCTION AND USE THEREOF The invention relates to a process for producing lubricating greases containing calcium lignin sulfonate, greases for lubrication of said type, and use thereof.

Lignin is a complex polymer based on the phenylpropane units, which is connected to one another with a wide variety of different chemical bonds. Lignin is present in plant cells along with cellulose and hemicellulose. Lignin itself is a linked macromolecule with average molecular weights of, for example, at least 10,000 g / mol (average weight).

There are basically 3 types of monolignol monomers that can be identified as components of lignin monomers, and differ in the degree of their methoxylation. They are p-coumaryl alcohol, coniferyl alcohol and sinapyl alcohol. These lignoles are incorporated into the structure of lignin in the form of hydroxyphenyl (H) -, guayacil (G) - and syringal (S) units. Seedless plants (gymnosperms), such as pine trees, mostly contain G units and a low proportion of H units. All lignins contain small amounts of incomplete or modified monolignoles. The primary function of lignins in plants is to provide mechanical stability through cross-linking of plant polysaccharides. Lignin constitutes about 1/3 of the dry mass of wood, and according to rough estimates of 30% of the mass of non-fossil organic carbon on Earth. It is the third most abundant organic material after cellulose and chitin, so it is very easy to access, renewable raw material for industrial products.

Lignin sulphonate is obtained as a byproduct of paper making by the sulfite process. In this process, the wood that has been reduced to wood chips is heated for about 7 to 15 hours in the presence of calcium sulfite liquor under pressure (for example 5 to 7 bar) and then the lignin sulfonic acid is removed from it. Lignocellulose in the form of calcium lignin sulfonate in a washing and precipitation process. The magnesium sulphide, sodium or ammonium salts alcohols can also be used in place of calcium hydrogen sulphite, and these produce the corresponding magnesium, sodium and lignin-sulfonic ammonium salts.

When the wash solution evaporates, the powdered lignin sulfonates remain. One-year global production of lignin sulfonates is of the order of 55 million tons.

Sodium, calcium and magnesium lignin sulphonates are often used as a raw material to plasticize and liquefy concrete and mortar. Lignin sulfonates are also used as pelletizing promoters in the artisanal animal food industry and as distributing or complexing agents in other fields.

In modern grease lubricant formulations, a non-negligible proportion of the formulation cost is devoted to tribochemically acting extreme pressure and anti-wear additives (EP / AW additive), with the result that they often become the controllers of prices for lubricating greases.

Many of these additives are produced in complicated, multi-step synthetic processes, and their use is limited both in terms of the nature of the application and its effective concentration in the final formulation due to the toxicological side effects that occur in many cases. In some applications, for example, in the case of constant speed axles or slow-moving assemblies and heavily loaded bearings, poor lubrication conditions and / or contact between the friction elements is inevitable even when the liquid additives are introduced. The prior practice, in such cases, was to use solid lubricants based on inorganic compounds (for example calcium and zinc phosphate salts), plastic powders (for example PTFE) or metal sulfides (for example MoS2). However, these components are also often expensive and can have a critical effect on the overall cost of a lubricant formulation.

The previous practice in the production of lubricating grease was the introduction of these additives in a second stage of the process, carried out after the actual chemical reaction process of the thickener formation. In this method, the additives, especially the solid lubricants, must be homogeneously distributed throughout the relatively viscous lubrication grease by the process of intense mixing and shearing with relatively high mechanical stress in order to obtain their optimum effect. From a modern perspective, the following has often proved unfavorable and led to the present invention.

Lubricating greases containing sodium lignin sulfonates and sodium soaps or lithium soaps are known from US 3239537 A. However, these are not suitable for use in the lubrication of constant speed joint shafts, mainly because fat attacks the TPE materials that are used in bellows.

Common additives lubricants and solid lubricants are usually based on non-renewable raw materials and are often poorly biodegradable.

On the other hand, the most common anti-wear additives and friction reduction lubricant additives involve costly chemical synthesis processes, which represent a significant cost factor. In particular, when solid lubricants are used for highly charged friction points, the most frequently used materials are relatively expensive, for example MoS2 or PTFE.

OBJECT / ADVANTAGE OF THE INVENTION The object of the invention is, therefore, to avoid the drawbacks of the prior art as described in the previous paragraph, and to make the lignin sulphonates available in lubricating greases as both cost-effective structure forming agents and as additives to promote strength. to wear, reduce friction and protect against aging, and at the same time provide lubricating greases of good water resistance.

The presence of lignin sulfonate means that the use of other common lubricant additives and solid lubricants, particularly MoS2, can be minimized or distributed in its entirety.

BRIEF DESCRIPTION OF THE INVENTION The invention is defined by the independent claims. Preferred variations represent the objects of the dependent claims or are described in the following.

According to the process on which the present invention is based, first a phase of precursors (base fat) is prepared by mixing at least - Oil base - Fatty acids and / or esters or salts thereof, wherein the fatty acid salt is at least partially, a calcium salt, for the production of soaps and containing at least calcium soaps, - Complex organic and / or inorganic agents, if necessary, - Alkaline torric hydroxides, in which the alkaline hóror hydroxides include at least CaOH - Water if necessary (for example as part of the hydroxides), and Ca-lignin sulfonate having average molecular weights (weight average) greater than 10000 g / mol. and heating to expel the components with low boiling point when using ethers, and to initiate at least one conversion of the alkaline earth hydroxide with the fatty acids and / or esters thereof and the lignin sulfonate, including reacting with the complexing agents before if the complexing agents before able to react with the alkali metal hydroxides are used to form a thickening structure in the base oil.

The components with low boiling point are those components that boil at temperatures of up to about 100 ° C under normal pressure, such as water or C1-C4 alcohols.

In order to produce the base-based fat, the mixture is preferably heated to temperatures above 120 ° C, or preferably above 180 ° C. The conversion based on grease is carried out in a heated reactor, which can also be constructed as an autoclave or vacuum reactor.

Then, in a second stage the formation of the thickener structure is completed by cooling and any additional components such as the additives and / or base oil are added to adjust to the desired consistency or the desired profile of properties. The second step can be carried out in the same reactor as that used for the first step, but it is preferable that the fat base is transferred from the reactor to a separate tank reactor for cooling and stirred to mix in the additional components , if any.

If necessary, the lubricating grease obtained in this way can be homogenized, filtered and / or degassed.

The preferred substances are Li / Ca-Ca / Li-, and the complex and normal soap thickened calcium fats to which lignin calcium sulfonate has already been added before the reaction phase to produce the base lubricant and is incorporated in the nominal lubricating grease structure through a thermal process in such a way that it is present in a highly homogeneous form, of insoluble oil and results in high melting point temperatures.

The use of alkaline ferrous salts, preferably calcium salts, both for the salts of fatty acids and the lignin sulfonate ensures that salt metathesis does not take place either during the production of the fat based on or during application.

Metathesis of salt, in particular with sodium salts, should be avoided in order to obtain a lubricating grease containing lignin sulfonate with good water resistance and at the same time a high drop temperature. For this reason, the use of sodium lignin sulfonate and sodium hydroxide should be avoided. Water resistance means that the grease is not emulsified with water and is adjusted to classification level 1-90 (test at 90 ° C) in the test according to DIN 51807-1 (version: 1979-1904 ). The water resistance is further understood to mean that the grease is adjusted to classification level 1-80 (test at 80 ° C) in the test in accordance with DIN 51807-2 (version 1990-1903).

The simultaneous application of an excess of alkali in the form of excess calcium hydroxide and possibly also calcium acetate or other calcium salts as the complexing agents is intended to ensure that even small residual amounts of sulphonic acid groups are neutralized in the lignin sulphonic acid and lose its hygroscopic water, emulsifier and the action that promotes corrosion. A high process temperature, above 120 ° C and especially above 180 ° C also ensures that the remaining moisture remaining in the lignin sulfonate evaporates out of the reaction medium completely and any other sulfonate component Lignin that have not been neutralized is neutralized by calcium hydroxide.

Standard lubricating oils that are liquid at room temperature are suitable for use as base oils. The base oil preferably has a kinematic viscosity of 20 to 2500 mm2 / s, in particular 40 to 500 mm2 / s, at 40 ° C.

The base oils can be classified as mineral oils or synthetic oils. Mineral oils that are eligible to be considered include, for example, basic naphthalene and kerosene basic mineral oils according to their classification in Group I API. Low aromatic, low-sulfur, chemically modified mineral oils have a small saturation fraction and better viscosity / temperature performance than Group I oils, classified as API Group II and III are also suitable.

As for the synthetic oils, polyethers, esters, polyalphaolefins, polyglycols and alkyl aromatics and mixtures thereof are noteworthy. The polyether compound may contain free hydroxyl groups, but may also be fully etherified or terminal esterified and / or may be produced from an initiator compound having one or more hydroxy groups and / or carboxyl groups (-COOH). Polyphenyl ethers, whether rented or not, are also possible as the only component, or better yet, as components of a mixture. Esters of a di-, tri- or aromatic tetracarboxylic acid with one or more of C2-C22 alcohols present in the mixture, alcohols, esters of adipic acid, sebacic acid, trimethylolpropane, pentaerythritol neopentyl Gli-col, or dipentaerythritol with aliphatic, branched or linear, C2 to C22 saturated or unsaturated carboxylic acids, esters of C18 dimer acids with C2 to C22 alcohols, complex esters, as individual components or in any mixture thereof, are also suitable for use.

The jones produced are either pure calcium soaps or mixtures containing calcium soaps, in addition to calcium soaps in particular lithium soaps and / or aluminum soaps of one or more saturated or unsaturated monocarboxylic acids having from 10 to 32 carbon atoms, substituted or not, in particular from 12 to 22 carbon atoms, with particular preference corresponding to 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. Even the corresponding low alcohol esters, such as corresponding triglycerides and methyl-, ethyl, propyl-, isopropyl-esters or sec. butyl acid esters of hydroxy acid, can be used with saponification instead of the free acid group to achieve a better dispersion.

The soap becomes a complex soap because of the presence of a complexing agent. The complex soaps containing grease lubricating compositions according to the invention (presence of a complexing agent) have high drop points, for example higher than 200 ° C (DIN ISO 2176). The amounts appropriate for the addition of the complexing agent are from 0.5 wt% to 20, particularly 0.5 to 10 wt%.

The following complexing agents are favorable for the purposes of the present invention: (a) alkali salt (preferably the lithium salt), except sodium salt, alkaline earth salt (preferably the calcium salt) or aluminum salt of a saturated or unsaturated monocarboxylic acid, or also hydroxycarboxylic acids having 2 to 8, particularly from 2 to 4 carbon atoms, or a dicarboxylic acid having from 2 to 16, particularly 2 to 12 carbon atoms, each of which may be substituted or unsubstituted, and / or (b) the alkaline earth and / or alkaline salt of boric acid and phosphoric acid or, in particular, the products of its reaction with LiOH and / or Ca (OH) 2 · The complexing agent (a) is preferably only a calcium salt, particularly if it is used as calcium acetate to produce the base fat. Acetic acid and propionic acid is particularly suitable for use as monocarboxylic acids. Acids such as hydroxybenzoic acid, parahydroxybenzoic acid, salicylic acid, 2-hydroxy-4-hexylbenzoic acid, metahydroxybenzoic acid, 2,5-dihydroxybenzoic acid (gentisic acid), 2,6-dihydroxybenzoic acid (gamma-resorcylic acid) or 4-hydroxybenzoic acid. hydroxy-4-methoxybenzoic acid are also suitable. Particularly suitable dicarboxylic acids are adipic acid (C6Hio04), sebacic acid (C10H18O4), azelaic acid (C9H16O4) and / or 3-tert-butyl-adipic acid (C10H18O4).

Possible substances for use as the borate (b) are included, for example meta-borate, diborate, tetraborate or orthoborate, such as monolithio orthoborate or calcium orthoborate. The phosphates can be selected from alkaline (preferably lithium) and alkaline (preferably calcium) earth dihydrogen phosphate, hydrogen phosphate, or pyrophosphate.

Optionally, bentonites, such as montmorillonite (in which some or all of the sodium ions may have been substituted with ammonium ions), aluminosilicates, clays, silicic acid (eg Aerosil), oil-soluble polymers (eg, polyolefins, poly (meth) acrylates, polyisobutylenes, polybutenes or PS) or also di and poly-ureas can also be used as co-thickening agents. The bentonites, aluminosilicates, clays, silicic acid and / or oil-soluble polymers can be added to produce the fat on the basis of a presentation or as additives later in the second step. The di- and poly-ureas can be introduced as additives.

The compounds according to the invention can also contain other additives as additional substances. Additional common substances for the purposes of the invention are antioxidants, antiwear agents, corrosion protection agents, detergents, colorants, lubrication enhancers, viscosity reducing additives, friction and high pressure additives.

Examples of such would be: - Antioxidants such as amine compounds (for example, alkylamines or 1-phenyl aminonaphthalene-), aromatic amines, for example phenyl-naphthyl amines or di-phenyl amines, phenolic compounds (for example, 2,6-di-tert-butyl) -4-methylphenol), sulfur antioxidants, zinc zinc dithiocarbamate or dithio-phosphate; - High pressure additives such as organic chlorine compounds, sulfur borate, phosphorus or calcium, zinc dithiophosphate, organic bismuth compounds; Substances intended to improve "oiliness", such as C2 to C6-polyols, fatty acids, esters of fatty acids or animal or vegetable oils; - Anticorrosive agents such as sulfonate oil, dinonylnaphthalene sulfonate or sorbitan esters; - Metal deactivators, such as sodium nitrite or benzotriazole; Viscosity enhancers, such as polymethacrylate, polyisobutylene, oligo-dec-l-enos, and polystyrenes; - Anti-wear additives and friction reducers such as organomolybdenum complexes (OMC), molybdenum-di-alkyl dithiophosphates, molybdenum-di-alkyl dithiocarbamates of molybdenum or di-alkyl dithiocar sulfide of bamates, particularly molybdenum-di-n-butyl dithiocarbamate and molybdenum disulfide-di-alkyl dithiocarbamate (Mo 20mSn (dialkyl carbamate) 2 where m = 0 to 3 and n = 4 to 1), - Friction reducers such as functional polymers, for example oleyl amides, polyether-amide and based organic compounds, for example polyethylene glycol tetradecylene alkyl glycol ether.

In addition, the lubricating grease compositions according to the invention also contain conventional additives for protection against corrosion, oxidation and attack by metals, which function as chelating compounds, radical scavengers, UV converters, layer forming reaction agents. and similar.

The solid lubricants can be selected, for example, from the group of polymer powders such as polyamides, polyimides or PTFE, graphite, metal oxides, boron nitride, metal sulphides, such as molybdenum sulphide, tungsten disulfide or mixtures of sulfur with tungsten, molybdenum, bismuth, tin and zinc base, inorganic salts of alkali and alkaline earth metals, such as calcium carbonate, sodium and calcium phosphates. Solid lubricants can be divided into the following four groups: compounds with a reticular layer structure, such as molybdenum disulfide and tungsten disulfide, graphite nitride, hexagonal boron and certain metal halides, oxidic and transition metal hydroxydic compounds alkaline torrids and carbonates or phosphates thereof; soft metals and / or plastics. The desired, advantageous lubricating properties can be adjusted with the use of lignin sulphonates with the need to use solid lubricants. In many cases, solid lubricants can be omitted altogether, or at least significantly reduced. If solid lubricants are used, graphite is the most favorable.

The lignin sulfonate may be chosen from calcium lignin sulphonates having a molecular weight (M w weight average) greater than 10,000, particularly greater than 12,000 or even higher than 15,000 g / mol, for example from 10,000 to 65,000 g / mol or 15,000 - 65,000 g / mol and in particular containing 2 to 12% by weight, particularly from 4 to 10% by weight, of sulfur (calculated as elemental sulfur) and / or 5 to 15% by weight, particularly 8 to 15% by weight Calcium weight (calculated Ca). In addition, calcium lignin sulphonates, other alkaline earth sulfonates of lignin may also be used. The average molecular weight (weight average) is determined, for example, by size exclusion chromatography. A suitable method is the SEC-shopping centers method as described in the article by GE Fredheim, Braaten SM and BE Christensen, "Comparison of molecular weight and molecular weight distribution of softwood and hardwood lignosulfonates" published in "Journal of Wood Chemistry and Technology ", vol. 23, No. 2, pages 197-215, 2003 and the article "The determination of the molecular weight of lignosulfonates by exclusion chromatography and multi-angle laser scattering" by the same authors, published in the "Publication on Chromatography A ", Volume 942, Edition 2.1, January 4, 2002, pages 191-199 (mobile phase: DMSO-SDS Phosphate, the stationary phase: Jordi-Glukose DVB-as described in section 2.5). Use of calcium lignin sulfonates are for example the commercially available products Norlig 11 D and Borrement Ca 120 produced by Borregard Lignotech. The lubricating grease according to the invention is characterized by the following composition: a) 55 to 92% by weight, particularly 70 to 85% by weight, base oil, b) 0 to 40% by weight, particularly 2 to 10% by weight, additives, c) 3 to 40% by weight, in particular 5 to 20% by weight, soaps, and d) 0 to 20% by weight or 0.5 to 20% by weight, particularly 0.5 to 10% by weight, complexing agents before, and e) excess of Ca (OH) 2, preferably 0.01 to 2% by weight , f) 0.5 to 50, particularly 2 to 15% by weight, and particularly preferably 3 to 8% by weight of lignin sulfonate, especially lignin calcium sulfonate, relative in each case to the overall composition, in which the components and their Preferred variants have been defined in the previous paragraph.

It was found that lignin sulfonates function as water-resistant structure forming agents, lubricating greases, which also have properties such as a solid lubricants or anti-wear additives and aging stabilizers. At the same time, the lignin sulfonate was observed to have synergistic effects with other surprisingly solid lubricants, for example with graphite or calcium carbonate.

It was also found that lignin sulfonates serve as multifunctional components for lubricants. Due to the large number of polar groups and aromatic structures they contain, their polymer structure and their low solubility in all types of lubricants-for oils, lignin sulphonates are suitable for use not only as a component thickener but also as solid lubricants in lubricating and lubricating greases. Its sulfur content also increases its EP / AW effect in lubricating greases and the phenolic structures provide an age inhibiting effect.

It is assumed that, due to the large amount of polymer and polar aromatic units it contains, the structure of lignin sulfonate is predominantly flat.

Consequently, they are able to be deposited very well in the layer structures on the low metal surfaces due to the effect of external friction forces and shear, being-cause the aromatic nuclei of the lignin sulfonate will enter into an associative Recip-Rocal action with the surface of the metal and the metallic friction associates are effectively and permanently separated from each other even with heavy loads and high pressures.

If the lignin calcium sulfonate is added before the start of the reaction phase during the production of soap thickeners, in particular complex calcium soaps, not only is the thickening effect of these improved soaps with a high drip point, But the anti-wear and lubrication protection effects of the corresponding formulations of grease lubricants are also improved. Accordingly, it is beneficial for the distribution and effect of the solid additives and lubricants if they are chemically or mechanically incorporated into the thickener structure as an additional structural element in situ during the reaction phase.

According to the prior art, it is necessary in many cases to use especially treated, expensive fatty acids, such as 12-hydroxystearic acid, or special complexing agents such as borates or salts of acetic acid, sebacic acid and azelaic acid for the manufacture of Soap greases with high drip points, however, these substances have little or no additional protection against wear and friction reduce additives. If lignin Ca-sulfonates are included, the use of these other components can be significantly reduced or even completely dispensed with. The use of lignin Ca-sulfonates also offers the ability to formulate high-performance lubricating greases on the basis of renewable raw materials and abandon a chemical additive-oriented that is harmful to the environment.

If oils consisting of unmodified or easily modified esters of fatty acids are native thickened the use of metallic soaps based on fatty acids of animal or vegetable origin, and if lignin sulfonates are used as the only additional thickener and at the same time the only additive component, are lubricating greases achieved that have been produced almost exclusively on the basis of renewable raw materials-Ies, with the sole exception of calcium hydroxide used for metallic soaps. These greases protect against aging and wear, and have the effect of raising the load crisis and reducing friction when lignin sulphonates are included as a thickener component.

The lubricating greases according to the invention are particularly suitable for use on or for joint constant speed shafts, bearings and gears.

If the base oils used consist of readily biodegradable esters, such as those containing mostly renewable raw materials, the lubricating greases are also suitable for the lubrication of total loss in the environmentally sensitive area (for example in mining or agriculture) .

In the special case of lubrication for joint constant free speed axles, the lubricating grease has first been formulated with calcium lignin sul-fonate which differs from the prior art in that it ensures a long operating life and good levels of efficiency totally without the use of MoS2 and other organic and inorganic molybdenum compounds.

The absence of other additives also serves to reduce the coefficient of friction, protect against loading seizures and wear and makes the product highly compatible with the materials used in standard commercial constant speed shaft sets bel low spots, such as rubber of chloroprene and polyether thermoplastic esters. Since sulfur contained in lignin sulphonate is bound by thermally stable sulfonate groups, unlike sulfur bound in conventional additives it is only released at very high temperatures and / or with very high levels of activation energies, as they do not occur in applications of grease lubrication except with tribocontacts under very high loads. In this manner, vulcanization or subsequent cross-linking of rubber materials by the sulfur released from lubricant aging is largely pre-perforated.

If the lignin calcium sulfonate is used in a lubricating grease formulation that has been adjusted with excess calcium hydroxide to be very basic, this prevents the sulphonic acid-free lignin from having a hydrolytic effect on the materials used in the Bel- low, such as thermoplastic polyether esters.

A special aspect of the present invention is that it can be used to obtain optimized cost for lubricating grease formulations to lubricate points that are under heavy load, such as in constant velocity joints, in particular, and that are well compatible with bellows containing , for example, esters of thermoplastic polyether (TPE) and chloroprene (CR), while offering a high degree of efficiency, low wear and a long service life.

Production examples Example A (comparative example): 958 g of tallow fatty acid, beef tallow 958 g, 958 g of calcium acetate, 27.7 g of TRISO-medium phosphate, 27,7 g of calcium borate and 358 g of calcium hydroxide were placed in a reactor in 12,000 g of a mixture of base oil and was 150 ml of water added. This base was heated to 198 ° C in a defined temperature program while stirring so that the added water and the water of reaction evaporated. The additives (see table) were added to the base at certain temperatures during the cooling phase. After the base was adjusted to the desired consistency by complement Ing. 3700 g of the base oil mixture, the final product is homogenized in a cogged gear mill. The grease thus obtained is suitable for use as a constant speed shaft grease joint, for example.

Example B: 460 g of tallow fatty acid, cow tallow 460 g of calcium acetate, 27.7 g TRISO-medium phosphate, 27.7 g of calcium borate and 168 g of calcium hydroxide and 920 g of lignin calcium sulfonate (Norlig 11D powder manufactured by Borregard Lignotech) were placed in a reactor in 14,000 g of a mixture of base oil and 150 ml of water was added. This base was heated to 208 ° C in a defined temperature program while stirring so that the water added and the evaporation-rated reaction water. Additives (see table) were added to the base at certain temperatures during the cooling phase. After the base was adjusted to the desired consistency by the addition of 3450 g of the base oil mixture, the final product is homogenized in a gear colloidal mill. The grease thus obtained is suitable for use as a constant speed shaft grease joint, for example.

Example C (comparative example): 800 g of 12-hydroxy stearic acid, 288 g of sebacic acid, 388 g of calcium acetate and calcium hydroxide 157. 3 g were placed in a reactor in 5000 g of a base oil mixture. 64 g of LiOH x H20 was dissolved in 250 ml of water and added. This base was heated to 200 ° C in a defined temperature program while stirring so that the added water and the water of reaction was evaporated. Additives were added to the base at certain temperatures during the cooling phase. After the base was adjusted to the desired consistency by the addition of 3116 g of the base oil mixture, the final product is homogenized in a gear colloidal mill. The fat thus obtained is suitable for use as bearing grease, for example.

Example D: 600 g of 12-hydroxy stearic acid, 216 g of sebacic acid, the acetate of 291 g of calcium and 720 g of calcium hydroxide and 300 g of lignin calcium sulfonate (Norlig powder 11D manufactured by Borregard Lignotech) were placed in a reactor in 5000 g of a base oil mixture. 48 g of LiOH x H20 was dissolved in 250 ml of water and added. This base was heated to 200 ° C in a defined temperature program while stirring-ring so that the added water and the water of reaction evaporated. Additives were added to the base at certain temperatures during the cooling phase.

After the base was adjusted to the desired consistency by the addition of 3116 g of the base oil mixture, the final product is homogenized in a gear colloidal mill. The fat thus obtained is suitable for use as bearing grease, for example.

Example E (comparative example): 1380 g of tallow fatty acid, beef tallow 1360 g, 80 g of trisodium phosphate, 80 g of calcium borate, 1400 g of calcium acetate and 493 g of calcium hydroxide were placed in a reactor in 12,000 g of a mixture of base oil and was 150 ml of added water. This base was heated to 230 ° C in a defined temperature program while stirring so that the added water and the water of reaction evaporated. Additives (see table) were added to the base at certain temperatures during the cooling phase. After the base was adjusted to the desired consistency by the addition of 3125 g of the base oil mixture, the final product is homogenized in a gear colloidal mill. The fat thus obtained is suitable for use as bearing grease, for example.

Example F: 1260 g of tallow fatty acid, beef tallow 1240 g, 80 g of trisodium phosphate, 80 g of calcium borate, calcium acetate 1,278 g, 493 g of calcium hydroxide and 885 g lignin calcium sulfonate (Powder Norlig 11D manufactured by Borregard Lignotech) were placed in a reactor in 12,000 g of a mixture of base oil and 150 ml of water was added.

This base was heated to 225 ° C in a defined temperature program while stirring-ring so that the added water and the water of reaction evaporated. Additives were added to the base at certain temperatures during the cooling phase. After the base was adjusted to the desired consistency by the addition of 3125 g of the base oil mixture, the final product is homogenized in a gear colloidal mill. The fat thus obtained is suitable for use as bearing grease, for example.

Example 6 (comparative example): 975 g of calcium-12 hydroxy stearate, 225 g of calcium acetate and 15 g of calcium borate were placed in a reactor in 3500 g methyl oleate ester. This base was heated to 200 ° C in a defined temperature program while stirring. Additives were added to the base at certain temperatures during the cooling phase. After the base was adjusted to the desired consistency by the addition of 180 g of oleate methyl ester, the final product is homogenized in a 3-roll mill. The lubricant grease thus obtained is made on the basis of predominantly renewable raw materials.

Example H: 841 g of calcium 12-hydroxy-stearate, 219.5 g of calcium acetate, 15 g of calcium BO-rate and 418 g of lignin calcium sulfonate (Powder Norlig 11D manufactured by Borregard Lignotech) were placed in a reactor in 1965 methyl oleate ester g. This base was heated to 200 0 C in a defined temperature program while stirring-ring. Additives were added to the base at certain temperatures during the friction phase. After the base was adjusted to the desired consistency by the addition of 1684 g of trimethylolpropane ester trioleate, the final product is homogenized in a 3-roll mill. The lubricant grease thus obtained is made on the basis of predominantly renewable raw materials.

Examples I and J: The products of example formulations I and J are similar to the production of example H but with the use of different amounts of calcium stearate-12-hydroxy, calcium acetate and lignin-calcium sulfonate and different compositions of ester-based oils. The grease lubricant thus obtained was made on the basis of predominantly renewable raw materials.

Table 1: Joint shaft grease formulations Ejeaplo D Reference Complex cospleple complex Description calcium calcium with 6% sulfanaco da with MoS2 lgnina 1. Thickener: 1. 1 Sulfonate of Lignin: Sulfonaco de lignna de Calcium 0.0 6.1 1. 2 Fatty Acids / -triglycerides: Acids gxuoi -. «« Ciated »4.B 2.0 Associated triglycerides« .a 2.6 1. 3 Hldróxldo álcali: Ca (OH) 2 í.a .S 1. Agent coaplej nte: Ca acecaco 4.0 2.0 Ca borato 0.1 O.S 2. Base oils: Basic mineral oil Mlado (to v40 * lOOsatVs) 79.5 00.B 3. Additives: Antioxidant 1 0.6 O.S AncinindsnCa 2 0.6 O.S Corrosion protection 0.5 0.2 Solid lubricant / graphite 0.5 1.0 LubricanCe solid, Me32 l.S 0.0 Total 100 100 4. Characteristics Unit Method 4. 1 Physical data general Penetration ao ciabajada DIH 130 213? 0.1 as 263 319 Panoexacién ao osabajada 60 double cycles DIM ISO 213? 0.1 m 351 340 Corrosion of charge 24 h HIT »1 / 100'C DIH 91811 evaluation 1-100 1-100 DQ Fusion Point) ISO 2176 • c 240 280 IB oil separation n / 40 * C DIN 51817 0.4 2.1 Oil separation 7 d / 40 * C DUl 5181? 2 8.9 4. 2 Resistance of Water Water resistance static 3 n / 90 * C DIN 51807-1 evaluation 1-90 1-90 level Loss of slave d to BO'C DIN 51T07-2 Evaluation 1 1 Table 1 (continued): Joint shaft grease formulations B Reference Complex complex invention of Description of calcium calcium with sulfonate with MoS2 lignin 6% 4. 3 Reduction of friction SRV at 80 ° C (40 Hz, l.S mm Amplitude, load SO OH) AS Til D DS707-05 Friction Coefficient 0.107 0.097 Stable stable process SK at 1S0 ° C (40Hz, l.Su Amplitude, charge SO OH) AS TU D D5707-05 Coefficient of friction 0.097 0.085 Stable stable process 4. 4 Protection against wear Welding load VKA DIN 51350-4 N 3400 3800 N enclosure VKA lOOON / l in DIN 51350-5 1.02 0.62 4. 5 Compatibility with protection bellows 4. 6.1 Chloroprene Inepsa 4012 168 h / 120 ° C -Reinforcement A DIN S3S05 -2 -1 -Change of volume DIN 53521 +3.5 -0.5 - Change in tensile force DIN 53504 * -0.5 -1.2 -Change in the elongation DIN S3S04 * -22.1 -19 4. 6.2 B rubber S E NBR 34 7d / 100 ° C DIN 53538-3 -Reinforcement A DIN 53505 -2 -3 -Change of volume DIN 53521 * +3.4 + 3.1 -Change in the tensile force DIN 53504 -2.9 - 5 -Change in elongation DIN 53504 -7.8 -4.5 4. 6.3 Klastomer TPE Hitrel 8332 336h / 12S ° C - Reinforcement D DIN 53505 -3 -2 -Change volume DIN 53521 + 13.1 + 6.2 -Change in the tensile force DIN 53504 * -32.9 + 6.7 -Change in elongation DIN 53504 -27 + 61 Amitel KB 463 336h / 12S ° C -Reinforcement D DIN 53505 -6 0 -Change of volume DIN 53521 + 10.7 +10.2 -Change in the tensile force DIN 53504 -15 -19.7 -Change in elongation DIN 53504 -10 + 7.8 4. 6.4 EPDH rubber Vamac Y76HR 336h / 12S ° C -Reinforcement A DIN 53505 +3 + 5 -Change of volume DIN 53521 * +6 + 0.3 -Change in the tensile force DIN 53504 t -17.4 -1.8 -Change in elongation DIN 53504 -39 - 35 5. Service life test on the shaft constant speed junction Deploys Service life (mili.) 13.6 11.

Stable state temperature average | c 41.1 38.

Table 2: Bearing grease formulations Reference Invention Reference Invention Complex Complex Complex Complex Description Calcium / lithium Calcium / lithium calcium calcium / lithium with 51 of with 51 sulfur of lignin sulfonate lignin 1. Eipeiadoi: 1. 1 Lignin Snlfanate: Calcium lignin sulfate 0.0 6.0 5.1 1. 2 Acids tiiglycerides: 12-HSA 8.0 5.0 Tensile degrees of acid 6.9 5.6 Triglyceride3 compounds 6.8 5.4 1. 3 Alkali hydroxide: Ii0i * H20 0.6 0.4 Ca | 0H) 2 1.6 1.0 2.5 2.0 1. 4 Ceplejante agent: Sebacic acid 2.9 1, 8 Ca acetate 3.9 2.4 7.0 5.7 Ca borate 0.4 0.3 2. Bate oils: Mixed basic buckthorn oil (in soVs) 81.6 82.0 75.6 75.3 3. Additives: Antioxidant 1 0.2 0.2 0.2 0.2 Antioxidant 2 0.2 0.2 0.2 0.2 Corrosion protection 1 1 0.4 0.3 total Table 2 (continued): Bearing grease formulations Ejesnlo D r Reference Invention Reference Invention Complex Complex Complex Complex Description Calcium / lithium calcium / lithium calcium calcium / lithium without 6i of with 51 lignin sulfonate sulfonate lignin 4. Feature »Unit method 4. 1 Details filióos genérale * Penetration not worked DIN ISO 2137 0.1 mra 299 27T 199 196 Penetration worked, 60 double cycles DIN ISO 2137 0.1 nm 310 299 234 242 Melting point DIN ISO 2176 206 230 255 > twenty Oil separation 18 h / 40'C DIN 51817 t 2.2 1.1 0 0 Oil separation 7 d / 40 * C DIN 51817 < 4.1 3.9 0.8 0. 6 .2 Water retention * Static water resistance Level of 3 h / 90 * C DIN 51807-1 evaluation 1-90 1-90 1-90 1-90 level Loss of washout at 80 * C DIN 51807-2 evaluation 1 1 1 1 .3 Corrosion protection level Distilled water Emcor DIN 51802 evaluation 0-0 0-0 0-0 0-0 4. 5 protection efficiency an ti wear Welding load VKA DIN 51350-4 N 2000 3400 2000 3200 enclosure VKA 1000N / tain DIN 51350-5 0.1 nm 0.91 0.45 0.89 0.67 5. Bearing tests PAG-FB9 (A / 1500/6000/120 * C) DIN51821-2 Average life of operation IOL 78 110 35 78 Average life of operation 150 115 220 74 156 Table 3: Foaming lubrication grease can oils from aatcila prtaa renewable Eíeaplo G H I J deference Invention Invention Involved Caplete of Spyglass Description calcium Cosplejo le calcium Calcium calcium complex 1. Espeiaoor: 1. 1 Lignin sulfonate: Calcium lignin sulfonate 0 7.1 9.9 * .l 1. 2 Jabonen tecalnadot: Ce- 12 Isterate hydro-i 19.5 14.1 19.8 10.1 1. 6 Corresponding Agent: to acetate 4.S 2.9 4.0 2.1 to borate 0.3 0.2 0.3 0.1 2. Oil, ugly »; Propane trioleate Ttineti lolhilol 28.5 ñetil oléate 73.. { 73.6 63.9 52.1 3. Additives: int oxidant 0.1 0.1 0. 1 0.1 Corrosion protection 2 2.0 2.0 2.0 total 100 100 ICO 100 1. Character íitlcai Method ttüdad 1. 1 General fljiros data Penetration not cracked PIN 190 2137 0.1 not 189 108 170 232 Penetration not worked, 60 cycles double DW 193 2137 0.1 m 221 209 219 301 Level of Copper corrosion Zlti / IDO'C PM 51811 evaluation 1-100 1-100 1-100 1- 100 Dropping point DW ISO 217 $ • C 210 250 248 205 Oil separation 18h 40 * C tm 51817 i 0.4 0.0 0.0 0.4 Oil separation 7d / 40'C DDI 51817 0.6 0.5 0. 1 2.5 4. 2 Resistance of agna Level of Static water resistance 3h / 90'C PW 51807-1 evaluation 1-90 1-90 1-90 1-90 4. 3 Corrosion protection Level of Igua distilled Encor PIN 51802 evaluation 1-1 1-1 1-1 1-1 1. 5 Antidetgute protection Welding load VKl ti »51350-4 N 2OO0 2800 3000 2400 VKi 1000N / 1 enclosure without PIN 51350-5 0. 1 m 0.89 0.67 0.54 0.48

Claims (24)

1. A process for producing lubricating greases containing lignin sulfonates comprising a) the step of mixing: - at least one base oil at least one calcium soap of a saturated or unsaturated monocarboxylic acid having carbon atoms 10 to 32, optionally substituted, - at least one complex agent selected from: (i) an alkali salt, with the exception of sodium salt, an alkaline earth salt or aluminum salt, of a saturated or unsaturated monocarboxylic acid or hydroxycarboxylic acids having 2 to 8, a dicarboxylic acid having 2 to 16 atoms of carbon, each of which optionally substituted, (ii) an alkali or alkaline earth salt of boric acid and / or phosphoric acid, including the reaction products thereof with LiOH and / or Ca (OH) 2, and (iii) mixtures thereof, and - at least calcium lignin sulfonate having average molecular weights (average weight) greater than 10,000 g / mol, heating above 120 ° C to initiate the reaction and exit of the components having lower melting point to produce a base fat, and b) the cooling step and adding base oil and possibly the additives while mixing.

2. The process according to claim 1, characterized in that in step a) calcium hydroxide is optionally added together with alkaline earth hydroxides.

3. The process according to claim 1, characterized in that the lubricating grease is adjusted for alkalinity, particularly by the addition of an excess amount of calcium hydroxide.

4. The process according to claim 1, characterized in that said heating takes place at higher temperatures of 180 ° C.

5. The process according to claim 1, characterized in that in step a) the lithium hydroxide, magnesium hydroxide and / or aluminum hydroxide and / or aluminum alcoholate and / or aluminum and / or lithium oxoalcoholate, magnesium and / or or aluminum soaps of a saturated or unsaturated monocarboxylic acid having 10 to 32 carbon atoms, optionally substituted, is also used in addition to calcium hydroxide.

6. The process according to claim 1, characterized in that the lubricating grease contains, independently of each: - 55 to 92 by weight%, particularly 70 to 85 by weight% base oil, - 0 to 40 by weight%, particularly 2 to 10 by weight% additives, - 3 to 40% by weight, particularly 5 to 20% by weight, calcium soaps and - 0.5 to 10 by weight% complexing agents, and - optionally excess Ca (OH) 2, preferably 0.01 to 2% by weight, and 0. 5 to 15% by weight, and particularly preferably 4 to 8% calcium lignin sulfonate, optionally further with other alkaline earth lignin sulphonates, relative in each case with the general composition of the lubricating grease.

7. The process according to claim 1, characterized in that the base grease of step a) can be produced by the use - 40 to 70 by weight%, particularly 45 to 60 by weight% base oil, - 10 to 60% by weight, particularly 15 to 50% by weight, calcium soaps, and - 5 to 30 weight% corapler agent, and optionally excess Ca (0H) 2, preferably 0.02 to 4% by weight, and 0. 7 to 30 by weight% calcium lignin sulfonate, optionally in addition with other alkaline earth lignin sulphonates, relative in each case with the composition of the base grease.

8. The process according to claim 1 or 4, characterized in that the base grease contains, independently from each other 0.2 - 5 by weight% graphite and / or no solid lubricant or less than < len weight% solid lubricant, particularly no M0S2.

9. The process according to claim 1, characterized in that the calcium soap is produced in-situ as a reaction by-product of calcium hydroxide with a saturated or unsaturated monocarboxylic acid having 10 to 32 carbon atoms, particularly having 16 to 20 carbon atoms, optionally substituted for example by hydroxy, as an ester or anhydride.

10. The process according to claim 1, characterized in that the complexing agent as a product of the reaction of a calcium salt, particularly calcium hydroxide, with a saturated or unsaturated monocarboxylic acid having 2 to 8, particularly 2 to 4 , carbon atoms or a dicarboxylic acid having 2 to 16, particularly 2 to 12 carbon atoms, each of which may or may not be substituted for example by hydroxyl as an ester or anhydride is added during step a).

11. The process according to claim 1, characterized in that the complexing agent is a calcium salt of a carboxylic acid and is produced in situ during step a) by the addition of a saturated or unsaturated monocarboxylic acid having 2 to 8 , particularly 2 to 4, carbon atoms or dicarboxylic acid having 2 to 16, particularly 2 to 12 carbon atoms, each of which may or may not be substituted for example by the hydroxyl as an ester or anhydride.

12. The process according to at least one of claims 1 to 11, characterized in that the calcium lignin sulfonate is dewatered at values less than 0.5% by weight of water before it is added, for example by heating in the base oil above 95 ° C, particularly above 100 ° C, for example 120 ° C.

13. The process according to at least one of claims 1 to 12, characterized in that the composition contains 0.5 to 20% by weight, particularly 0.5 to 10% of the complexing agent.

14. A lubricating grease compound containing - 55 to 92% by weight, particularly 70 to 85% by weight, base oil, - 0 to 40% by weight, particularly 2 to 10% by weight, additives, - 3 to 40 by weight%, particularly 5 to 20 by weight%, calcium soaps of a saturated or unsaturated monocarboxylic acid having 10 to 32 carbon atoms, optionally substituted - 0.5 to 10 by weight% complexing agent, selected from (i) an alkali salt, with the exception of the sodium salt, an alkaline earth salt or aluminum salt of a saturated or unsaturated monocarboxylic acid or hydroxycarboxylic acids having 2 to 8, a dicarboxylic acid having 2 to 16 carbon atoms , each of which is optionally substituted, (ii) an alkali or earth alkaline salt of boric acid and / or phosphoric acid, including the reaction products thereof with LiOH and / or Ca (OH) 2, optionally excess Ca (0H) 2, preferably 0.01 to 2 in weight%, and (iii) the mixtures thereof, and 0. 5 to 15% by weight, and particularly preferably 2 to 8% by weight of calcium lignin sulfonate, possibly in addition to other alkaline earth lignin sulphonates, relative in each case to the total composition of the lubricating grease, wherein the compound comprises a cone penetration value (worked penetration) of 265 to 385 mm / 10 (at 25 ° C), determined in accordance with ISO 2137.

15. The composition according to claim 14, characterized in that the composition comprises a cone penetration value (worked penetration) of 285 to 355 mm / 10, determined in accordance with ISO 2137.

16. The composition according to at least one of claims 14 or 15, characterized in that the base oil has a kinematic viscosity of 20 to 2500 mm2 / s, preferably 40 to 500 mm2 / s, at 40 ° C.

17. The composition according to at least one of claims 14 to 16, characterized in that the complexing agent consists of: - alkali salt, preferably lithium salt, alkaline earth salt, preferably calcium salts or aluminum salt of a saturated or unsaturated monocarboxylic acid having 2 to 8, particularly 2 to 4 carbon atoms or a dicarboxylic acid having 2 to 16, particularly 2 to 12, carbon atoms, each of which is optionally substituted.

18. The composition according to at least one of claims 14 to 17, characterized in that the additive comprises one or more members selected from the following group: amino compounds, phenol compounds, sulfur antioxidants, zinc dithiocarbamate or zinc dithiophosphate as antioxidants; - compounds of organic chloride, sulfur, phosphorus or calcium borate, zinc dithiophosphate, organic bismuth compounds as high-pressure additives; - C2- to C6- polyols, fatty acids, fatty acid esters or animal or vegetable oils; Petroleum sulphonate, dinonylnaphthalene sulfonate or sorbitan ester as anticorrosive agents. benzotriazole or sodium nitrate as metal neutralizers; - polymethacrylate, polyisobutylene, oligo-dec-1-enos and polystyrenes as viscosity improvers; dithiocarbamates dialkyls molybdenum or dialkyl dithiocarbamates sulfides molybdenum or aromatic amines as anti-wear additives; functional polymers, for example oleyl amides, polyether organic compounds and based on amido or dithiocarbamate molybdenum as friction modifiers, and - polymer powders such as polyamides, polyimides or PTFE, graphite, metal oxides, boron nitride, metal sulphides such as molybdenum disulfide, tungsten disulfide or sulphides mixed with tungsten, molybdenum, bismuth, tin and zinc base, inorganic salts of alkaline and alkaline toric metals, such as calcium carbonate, sodium and calcium phosphates as solid lubricants.

19. The composition according to at least one of claims 14 to 18, characterized in that the lubricating grease is water resistant, particularly a) in accordance with the test defined in DIN 51807-1, evaluation level 1-90, and / or b) according to the test defined in DIN 51807-2, evaluation level 1-80.

20. The composition according to at least one of claims 14 to 19, characterized in that the calcium lignin sulfonate has an average molecular weight (Mw, average weight) of more than 10,000, particularly more than 12,000 or even more than 15,000 g / mol, and independently thereof contains 2 to 12 by weight%, particularly 4 to 10 by weight%, sulfur (calculated as sulfur element) and / or also independently 5 to 15% by weight, particularly 8 to 15% by weight of calcium.

21. The composition according to at least one of claims 14 to 20, characterized in that the lubricating grease contains a base oil made on the basis of renewable raw materials AND / or fraction of 95% or more thereof is made based on renewable raw materials.

22. The composition according to at least one of claims 14 to 20, characterized in that the composition has a melting point higher than 200 ° C in accordance with DIN ISO 2176.

23. The use of the composition according to at least one of claims 14 to 22 for lubricating at least one transmission.

24. The use of the composition according to at least one of claims 14 to 22 for lubricating the lubrication points in constant velocity joints having a shaft attachment sleeve constructed from thermoplastic polyester esters as the sheath material shaft union.