EP2531587B9 - Schmierfette enthaltend ligninsulfonat, deren herstellung und verwendung - Google Patents

Schmierfette enthaltend ligninsulfonat, deren herstellung und verwendung Download PDF

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Publication number
EP2531587B9
EP2531587B9 EP11711018.9A EP11711018A EP2531587B9 EP 2531587 B9 EP2531587 B9 EP 2531587B9 EP 11711018 A EP11711018 A EP 11711018A EP 2531587 B9 EP2531587 B9 EP 2531587B9
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Prior art keywords
weight
calcium
acid
salt
carbon atoms
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German (de)
English (en)
French (fr)
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EP2531587A1 (de
EP2531587B1 (de
Inventor
Thomas Litters
Alexander Liebenau
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Fuchs SE
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Fuchs Petrolub SE
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Priority to SI201130721T priority Critical patent/SI2531587T1/sl
Priority to PL11711018T priority patent/PL2531587T3/pl
Publication of EP2531587A1 publication Critical patent/EP2531587A1/de
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Publication of EP2531587B1 publication Critical patent/EP2531587B1/de
Priority to HRP20160072TT priority patent/HRP20160072T1/hr
Publication of EP2531587B9 publication Critical patent/EP2531587B9/de
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M135/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing sulfur, selenium or tellurium
    • C10M135/08—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing sulfur, selenium or tellurium containing a sulfur-to-oxygen bond
    • C10M135/10—Sulfonic acids or derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M141/00—Lubricating compositions characterised by the additive being a mixture of two or more compounds covered by more than one of the main groups C10M125/00 - C10M139/00, each of these compounds being essential
    • C10M141/08—Lubricating compositions characterised by the additive being a mixture of two or more compounds covered by more than one of the main groups C10M125/00 - C10M139/00, each of these compounds being essential at least one of them being an organic sulfur-, selenium- or tellurium-containing compound
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M159/00—Lubricating compositions characterised by the additive being of unknown or incompletely defined constitution
    • C10M159/12—Reaction products
    • C10M159/20—Reaction mixtures having an excess of neutralising base, e.g. so-called overbasic or highly basic products
    • C10M159/24—Reaction mixtures having an excess of neutralising base, e.g. so-called overbasic or highly basic products containing sulfonic radicals
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2201/00—Inorganic compounds or elements as ingredients in lubricant compositions
    • C10M2201/04—Elements
    • C10M2201/041—Carbon; Graphite; Carbon black
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2201/00—Inorganic compounds or elements as ingredients in lubricant compositions
    • C10M2201/06—Metal compounds
    • C10M2201/065—Sulfides; Selenides; Tellurides
    • C10M2201/066—Molybdenum sulfide
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/10—Carboxylix acids; Neutral salts thereof
    • C10M2207/12—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms
    • C10M2207/125—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of eight up to twenty-nine carbon atoms, i.e. fatty acids
    • C10M2207/127—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of eight up to twenty-nine carbon atoms, i.e. fatty acids polycarboxylic
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2010/00—Metal present as such or in compounds
    • C10N2010/02—Groups 1 or 11
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2010/00—Metal present as such or in compounds
    • C10N2010/04—Groups 2 or 12
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/02—Pour-point; Viscosity index
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/06—Oiliness; Film-strength; Anti-wear; Resistance to extreme pressure
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/12—Inhibition of corrosion, e.g. anti-rust agents or anti-corrosives
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/26—Waterproofing or water resistance
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/36—Seal compatibility, e.g. with rubber
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/02—Bearings
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2050/00—Form in which the lubricant is applied to the material being lubricated
    • C10N2050/10—Semi-solids; greasy

Definitions

  • the invention relates to a process for the preparation of calcium lignosulfonate greases, such lubricating greases and their use
  • Lignin is a complex polymer based on phenylpropane units, which are interlinked with each other with a range of different chemical bonds. Lignin occurs in plant cells together with cellulose and hemicellulose. Lignin itself is a cross-linked macromolecule with average molecular weights of e.g. greater than 10,000 g / mol (weight average).
  • lignin As monomer building blocks of lignin, essentially 3 types of monolignol monomers can be identified, which differ from each other in the degree of methoxylation. These are p- cumaryl alcohol, coniferyl alcohol, and sinapyl alcohol. These lignols are incorporated into the lignin structure in the form of hydroxyphenyl (H), guaiacyl (G), and syn-ring (S) units. Muscovy plants (Gymnosperms), such as pine trees, contain overwhelmingly G units and small amounts of H units. All lignins contain small amounts of incomplete or modified monolignols. The primary function of lignins in plants is to provide mechanical stability by cross-linking the plant polysaccharides. Lignin represents about 1/3 of the dry mass of wood and roughly represents 30% of the non-fossil organic carbon mass on Earth. It is the third most common organic material after cellulose and chitin and thus also a very readily available renewable raw material for industrial products
  • Lignosulfonate is a by-product of papermaking with the sulfite process.
  • chopped wood is heated to chips under pressure (eg 5 to 7 bar) for about 7 to 15 hours in the presence of calcium hydrogen sulphite solution and then the lignosulphonic acid in the form of calcium lignosulphonate is removed from the lignocellulose by a washing and precipitation process.
  • calcium hydrogen sulfite it is also possible to use magnesium, sodium or ammonium sulfite bases, which leads to the corresponding magnesium, sodium and ammonium salts of lignin sulfonic acid.
  • lignosulfonates are widely used as a base for the plasticization and liquefaction of concrete and mortar. Another use find lignosulfonates as Pelletierangesmittel in the concentrated feed industry and in other areas as a dispersant or complexing agent.
  • Tribochemically acting extreme pressure (high pressure) and anti-wear (EP / AW) additives used in today's grease formulations account for a not inconsiderable amount of the formulation costs and are thus often the price-driving factor for greases.
  • Common lubricant additives and solid lubricants are usually not based on renewable resources and are often difficult to biodegrade.
  • most common wear protection additives and friction-reducing lubricant additives require a complex synthetic chemistry and therefore represent a major cost factor. Therefore, especially when using solid lubricants for highly loaded friction points dominate comparatively expensive materials such as MoS 2 or PTFE.
  • the object of the invention is thus to avoid the disadvantages of the prior art described above, and to provide lignosulfonates both as a cost structurant and as a wear-protective, friction-reducing and anti-aging additive in lubricating greases and at the same time to provide good water resistance of the greases.
  • Low boiling components are those components which boil at up to about 100 ° C at normal pressure, such as water or C 1 to C 4 alcohols.
  • the base fat Preferably, to produce the base fat to temperatures of about 120 ° C or better above 180 ° C heated.
  • the conversion to the base fat takes place in a heated reactor, which can also be designed as an autoclave or vacuum reactor.
  • a second step by cooling the formation of the thickener structure is completed and, if appropriate, further constituents, such as additives and / or base oil, are added to set the desired consistency or the desired property profile.
  • the second step may be carried out in the reactor of the first step, but preferably the base grease from the reactor is transferred to a separate stirred tank for cooling and mixing in the optional further constituents.
  • the resulting grease is homogenized, filtered and / or vented.
  • Ca / Li, Li / Ca and calcium thickened normal and complex soap fats are preferably used, in which calcium lignosulfonate is added even before the reaction phase to produce the base fat and incorporated into the grease structure by way of a thermal process in such a way that is very homogeneous oil-insoluble form and leads to high dropping point temperatures.
  • alkaline earth salts preferably calcium salts
  • lignosulfonate ensures that no salification takes place both in the preparation of the base fat and in the application.
  • the salification, in particular to the sodium salts, must be prevented in order to obtain a lignosulfonate-containing grease with good water resistance and at the same time a high dropping point. Therefore, avoid the use of sodium lignosulfonate and sodium hydroxide.
  • the fat is not emulsified by water according to the test according to DIN 51807-1 (Issue: 1979-04) or the evaluation level 1-90 (test at 90 ° C) corresponds.
  • Water resistance is also understood to mean that the grease according to the test according to DIN 51807-2 (1990-03 edition) corresponds to the evaluation level 1-80 (test at 80 ° C.).
  • Suitable base oils are customary lubricating oils which are liquid at room temperature.
  • the base oil preferably has a kinematic viscosity of 20 to 2500 mm 2 / s, in particular 40 to 500 mm 2 / s at 40 ° C.
  • the base oils can be classified as mineral oils or synthetic oils.
  • Mineral oils are, for example, considered to be naphthenic and paraffinic mineral oils according to API Group I classification.
  • Synthetic oils which may be mentioned are polyethers, esters, polyalphaolefins, polyglycols and alkylaromatics and mixtures thereof.
  • the polyether compound may have free hydroxyl groups, but may also be fully etherified or end groups esterified and / or prepared from a starting compound having one or more hydroxy and / or carboxyl groups (-COOH).
  • esters of an aromatic di-, tri- or tetracarboxylic acid C2- to C22-alcohols present in or in a mixture
  • esters of adipic acid, sebacic acid trimethylolpropane, neopentyl glycol, pentaerythritol or dipentaerythritol with aliphatic branched or unbranched, saturated or unsaturated C2 to C22-carboxylic acids, C18 dimer acid esters with C2 to C22 alcohols, complex esters, as individual components or in any desired mixture.
  • the soaps produced are either pure calcium soaps or mixtures containing calcium soaps, in particular besides calcium soaps also lithium soaps and / or aluminum soaps, one or more saturated or unsaturated mono-carboxylic acids with 10 to 32 carbon atoms, optionally substituted, in particular with 12 to 22 carbon atoms, particularly preferred 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.
  • the free acid group and corresponding lower alcohol esters can be used with saponification, z.
  • the soap becomes a complex soap by the presence of a complexing agent.
  • the lubricating grease compositions according to the invention containing complexing soaps (presence of a complexing agent) have increased dropping points, for example greater than 200 ° C. (DIN ISO 2176).
  • the complexing agent to 0.5 to 20 wt.%, In particular 0.5 to 10 wt.% Used.
  • the complexing agent (a) is preferably exclusively a calcium salt, in particular if it is used as calcium acetate for the preparation of the base fat.
  • Particularly suitable mono-carboxylic acids are acetic acid and propionic acid.
  • hydroxybenzoic acids such as parahydroxybenzoic acid, salicylic acids, 2-hydroxy-4-hexylbenzoic acid, metahydroxybenzoic acid, 2,5-dihydroxybenzoic acid (gentisic acid), 2,6-dihydroxybenzoic acid (gammaresorcylic acid) or 4-hydroxy-4-methoxybenzoic acid.
  • 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 ).
  • borate (b) for example, metaborate, diborate, tetraborate or orthoborate, e.g. Monolithium orthoborate or calcium orthoborate.
  • Suitable phosphates are alkali metal (preferably lithium) and alkaline earth metal (preferably calcium) dihydrogen phosphate, hydrogen phosphate, or pyrophosphate.
  • bentonites such as montmorillonite (whose sodium ions may be exchanged or partially exchanged with ammonium ions), aluminosilicates, clays, silicic acid (eg Aerosil), oil-soluble polymers (eg polyolefins, poly (meth) acrylates, polyisobutylenes, polybutenes, may additionally be added or PS) or di- and polyureas are used as co-thickener.
  • the bentonites, aluminosilicates, clays, silicic acid and / or oil-soluble polymers may be added to make the base fat or added later as an additive in the second step.
  • the di- and polyureas can be added as an additive.
  • compositions according to the invention optionally further contain additives as additives.
  • additives in the context of the invention are antioxidants, anti-wear agents, corrosion inhibitors, detergents, dyes, lubricity improvers, viscosity additives, friction reducers and high-pressure additives.
  • the grease compositions of this invention contain conventional anti-corrosive, oxidative, and anti-metallope additives which act as chelates, radical scavengers, UV transducers, reaction layer formers, and the like.
  • solid lubricants may, for example, polymer powder such as polyamides, polyimides or PTFE, graphite, metal oxides, boron nitride, metal sulfides such as molybdenum disulfide, tungsten disulfide or mixed sulfides based on tungsten, molybdenum, bismuth, tin and zinc, inorganic salts of alkali and alkaline earth metals, such as calcium Carbonate, sodium and calcium phosphates are used.
  • polymer powder such as polyamides, polyimides or PTFE, graphite, metal oxides, boron nitride, metal sulfides such as molybdenum disulfide, tungsten disulfide or mixed sulfides based on tungsten, molybdenum, bismuth, tin and zinc
  • metal sulfides such as molybdenum disulfide, tungsten disulfide or mixed sul
  • Solid lubricants can be divided into the following four groups: layered structure compounds such as molybdenum disulfide and tungsten disulfide, graphite, hexagonal boron nitride, and some metal halides; oxidic and hydroxidic compounds of the transition and alkaline earth metals or their carbonates or phosphates; soft metals and / or plastics.
  • the desired advantageous lubrication properties can be adjusted by the use of lignosulfonates, without having to use solid lubricants. In many cases, these can be dispensed with completely or at least can be significantly minimized. As far as solid lubricants are used graphite can be used advantageously.
  • lignosulfonate calcium lignosulfonates having a molecular weight (Mw, weight average) of greater than 10,000, in particular greater than 12,000 or even greater than 15,000 g / mol are used, for example from greater than 10,000 to 66,000 g / mol or 16,000-65,000 g / mol, which in particular 2 to 12% by weight, in particular 4 to 10% by weight, of sulfur (calculated as elemental sulfur) and / or 5 to 15% by weight, in particular 8 to 15% by weight of calcium (calculated Ca).
  • Mw molecular weight
  • the weight average molecular weight is determined, for example, by size exclusion chromatography.
  • a suitable method is the SEC-MALLS method as described in the article by GE Fredheim, SM Braaten 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 " Molecular weight determination of lignosulfonates by size exclusion chromatography and multi-angle laser scattering "of the same authors, published in Journal of Chromatography A, Volume 942, Issue 1-2, 4 January 2002, pages 191-199 (Mobile phase: phosphate-DMSO-SDS, stationary phase: Jordi-glucose DVB as described under 2.5).
  • Suitable calcium lignosulfonates are, for example, the commercially available products Norlig 11 D and Borrement Ca 120 from Borregard Lignotech.
  • the lubricating grease according to the invention is characterized by the features of claim 14 and the lubricating grease, as used in the method according to the invention, by the preferred features of claim 6.
  • lignosulfonates act as structure formers for water-resistant lubricating greases with simultaneous properties as solid lubricant or wear protection additive and aging stabilizer.
  • surprisingly synergistic effects of lignin sulfonate with other solid lubricants e.g. observed with graphite or calcium carbonate.
  • lignosulfonates are multifunctional components for lubricants. Due to their high number of polar groups and aromatic structures, their polymeric structure and their low solubility in all types of lubricating oils, lignosulfonates are not only suitable as thickener constituents but also as solid lubricants in lubricating greases and lubricating pastes. In addition, the sulfur content promotes the EP / AW effect in the lubricating greases and the phenolic structures provide an age-inhibiting effect.
  • the lignosulfonate structure has a predominantly planar structure due to its large number of polymeric and polar aromatic units.
  • Thickening oils consisting of unmodified or slightly modified native fatty acid esters with metal soaps based on animal or vegetable fatty acids and lignosulfonates used as the only other thickener and simultaneous additive component, we obtain greases, except for the calcium hydroxide used for metal soaps exclusively based on renewable Raw materials were produced. These are resistant to aging and wear, as well as increasing the load stress and reducing friction by the use of lignosulfonates as thickener component.
  • the greases according to the invention are particularly suitable for use in or for constant velocity universal joint, rolling bearings and gearbox.
  • the lubricating greases are also suitable for loss lubrication in the environmentally sensitive field (for example in mining or agriculture).
  • TPE thermoplastic polyetheresters
  • CR chloroprenes
  • the final product was homogenized on a toothed colloid mill.
  • the fat thus obtained is e.g. suitable as constant velocity universal joint grease.
  • the final product was homogenized on a toothed colloid mill.
  • the fat thus obtained is e.g. suitable as rolling bearing grease.
  • the batch was heated in a predetermined temperature program to 225 ° C with stirring, thereby evaporating the added water and the water of reaction.
  • additives were added to the batch at certain temperatures.
  • the final product was homogenized on a Zahnkolloidmühle.
  • the fat thus obtained is e.g. suitable as rolling bearing grease.
  • methyl oleate ester Into a reactor, 3500 g of methyl oleate ester, 975 g of calcium 12-hydroystearate, 225 g of calcium acetate and 15 g of calcium borate were charged. The batch was heated in a predetermined temperature program to 200 ° C with stirring. In the cooling phase, additives were added to the batch at certain temperatures. After adjusting the batch to the desired consistency by adding 180 g of methyl oleate ester, the final product was homogenized on a 3-roll mill. The resulting grease is based on predominantly renewable raw materials.
  • Methyloleate ester 841 g calcium 12-hydroystearate, 219.5 g calcium acetate, 15 g calcium borate and 418 g calcium lignosulfonate (Norlig 11 D powder from Borregard Lignotech) were introduced into a reactor in 1965 g.
  • the batch was heated in a predetermined temperature program to 200 ° C with stirring. In the cooling phase, additives were added to the batch at certain temperatures. After adjusting the batch to the desired consistency by adding 1684 g of trimethylolproprantrioleate ester, the final product was homogenized on a 3-roll mill. The resulting grease is based on predominantly renewable raw materials.
  • Example Formulations I and J correspond to the preparation of Example H using different amounts of calcium 12-hydroxy stearate, calcium acetate and calcium lignin sulfonate, as well as different compositions of ester base oils.
  • the greases obtained in this way are based on predominantly renewable raw materials.
  • Table 1 Cardan shaft grease formulations ⁇ / b> example A B reference invention description Calcium complex Calcium complex with MoS2 with 6% lignosulfonate 1.
  • Characteristics method unit 4.1 General physical data Penetration forfeited DIN ISO 2137 0.1mm 263 315 Penetration rolled 60 double acts DIN ISO 2137 0.1mm 351 340 Copper corrosion 24h / 100 ° C DIN 51811 Rank 1-100 1-100 Dropping point DIN ISO 2176 ° C 240 280 Oil separation 18h / 40 ° C DIN 51817 % 0.4 2.1 Oil separation 7d / 40 ° C DIN 51817 % 2 8.9 4.2 Water resistance static water resistance 3h / 90 ° C DIN 51807-1 Rank 1-90 1-90 Washout loss at 80 ° C DIN 51807-2 Rank 1 1 4.3 Reduction of friction SRV at 80 ° C (40Hz, 1.5mm amplitude, 500N load) ASTM D D5707-05 friction 0,107 0.097 course calm calm SRV at 150 ° C (40Hz, 1.5mm amplitude, 500N load) ASTM D D5707-05 friction 0.097 0.085 course calm calm 4.4 Wear protection effect VKA
  • lignosulfonate calcium ligninsulfonate 0.0 6.0 0 5.1 1.2 fatty acids / triglycerides: 12-HSA 8.0 5.0 mixed fatty acid 6.9 5.6 Mixed triglyceride 6.8 5.4 1.3
  • Alkali Hydroxide LiOH * H2O 0.6 0.4 Ca (OH) 2 1.6 1.0 2.5 2.0 1.4
  • Complexing agent sebacic 2.9 1.8 Ca acetate 3.9 2.4 7.0 5.7 Ca-borate 0.4 0.3 2.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Chemistry (AREA)
  • Lubricants (AREA)
  • Sliding-Contact Bearings (AREA)
  • General Details Of Gearings (AREA)
  • Rolling Contact Bearings (AREA)
EP11711018.9A 2010-02-02 2011-01-31 Schmierfette enthaltend ligninsulfonat, deren herstellung und verwendung Active EP2531587B9 (de)

Priority Applications (3)

Application Number Priority Date Filing Date Title
SI201130721T SI2531587T1 (sl) 2010-02-02 2011-01-31 Maziva, ki vsebujejo lignosulfonat, proizvodnja in uporaba le-teh
PL11711018T PL2531587T3 (pl) 2010-02-02 2011-01-31 Środki smarne zawierające ligninosulfonian, ich wytwarzanie i zastosowanie
HRP20160072TT HRP20160072T1 (hr) 2010-02-02 2016-01-22 Masti za podmazivanje koje sadrže ligninsulfonat, njihova proizvodnja i primjena

Applications Claiming Priority (2)

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DE102010006745A DE102010006745A1 (de) 2010-02-02 2010-02-02 Schmierfette enthaltend Ligninsulfonat, deren Herstellung und Verwendung
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DE102010006745A1 (de) 2011-08-04
PL2531587T3 (pl) 2016-06-30
JP2013518929A (ja) 2013-05-23
RU2012136909A (ru) 2014-03-10
RS54610B1 (en) 2016-08-31
EP2531587A1 (de) 2012-12-12
KR101833854B1 (ko) 2018-03-05
AU2011212763B2 (en) 2013-10-17
HUE026690T2 (en) 2016-07-28
DK2531587T3 (en) 2016-01-25
EP2531587B1 (de) 2015-11-04
CA2788157C (en) 2018-06-26
KR20120139730A (ko) 2012-12-27
PT2531587E (pt) 2016-02-26
JP5856078B2 (ja) 2016-02-09
MX2012008960A (es) 2012-10-15
BR112012019181B1 (pt) 2018-09-11
BR112012019181A2 (pt) 2018-03-27
CA2788157A1 (en) 2011-08-11
US20120302472A1 (en) 2012-11-29
ES2561821T3 (es) 2016-03-01
SI2531587T1 (sl) 2016-04-29
RU2554873C2 (ru) 2015-06-27
CN102770513B (zh) 2015-09-30
HRP20160072T1 (hr) 2016-04-08
WO2011095155A1 (de) 2011-08-11
CN102770513A (zh) 2012-11-07
AU2011212763A1 (en) 2012-09-06

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