HUE026690T2 - Lubricating greases containing lignosulfonate, the production thereof, and the use thereof - Google Patents

Lubricating greases containing lignosulfonate, the production thereof, and the use thereof Download PDF

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Publication number
HUE026690T2
HUE026690T2 HUE11711018A HUE11711018A HUE026690T2 HU E026690 T2 HUE026690 T2 HU E026690T2 HU E11711018 A HUE11711018 A HU E11711018A HU E11711018 A HUE11711018 A HU E11711018A HU E026690 T2 HUE026690 T2 HU E026690T2
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weight
calcium
acid
salt
base
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HUE11711018A
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Hungarian (hu)
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Thomas Litters
Alexander Liebenau
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Fuchs Petrolub Se
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    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M135/00Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing sulfur, selenium or tellurium
    • C10M135/08Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing sulfur, selenium or tellurium containing a sulfur-to-oxygen bond
    • C10M135/10Sulfonic acids or derivatives thereof
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M141/00Lubricating 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
    • C10M141/08Lubricating 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
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M159/00Lubricating compositions characterised by the additive being of unknown or incompletely defined constitution
    • C10M159/12Reaction products
    • C10M159/20Reaction mixtures having an excess of neutralising base, e.g. so-called overbasic or highly basic products
    • C10M159/24Reaction mixtures having an excess of neutralising base, e.g. so-called overbasic or highly basic products containing sulfonic radicals
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2201/00Inorganic compounds or elements as ingredients in lubricant compositions
    • C10M2201/04Elements
    • C10M2201/041Carbon; Graphite; Carbon black
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2201/00Inorganic compounds or elements as ingredients in lubricant compositions
    • C10M2201/06Metal compounds
    • C10M2201/065Sulfides; Selenides; Tellurides
    • C10M2201/066Molybdenum sulfide
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/10Carboxylix acids; Neutral salts thereof
    • C10M2207/12Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms
    • C10M2207/125Carboxylix 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
    • C10M2207/127Carboxylix 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
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10NINDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2010/00Metal present as such or in compounds
    • C10N2010/02Groups 1 or 11
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10NINDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2010/00Metal present as such or in compounds
    • C10N2010/04Groups 2 or 12
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10NINDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/02Pour-point; Viscosity index
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10NINDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/06Oiliness; Film-strength; Anti-wear; Resistance to extreme pressure
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10NINDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/12Inhibition of corrosion, e.g. anti-rust agents or anti-corrosives
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10NINDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/26Waterproofing or water resistance
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10NINDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/36Seal compatibility, e.g. with rubber
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10NINDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00Specified use or application for which the lubricating composition is intended
    • C10N2040/02Bearings
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10NINDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2050/00Form in which the lubricant is applied to the material being lubricated
    • C10N2050/10Semi-solids; greasy

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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)
  • Rolling Contact Bearings (AREA)
  • Sliding-Contact Bearings (AREA)
  • General Details Of Gearings (AREA)

Description

The invention relates to a process fór producing lubricating greases that contain calcium lignin sulfonate, iutfocatlng greases of such kind, and use thereof.
Lignin is a complex polymer based on phenylpropane units, which are cross -linked to each other with a wide variety of different chemicai bonds. Lignin is present In plant cells together with cellulose and hemieeltelose. Lignin itself Is a cross-linked macromolecule with average molecular weights of for example at least 10,000 g/mol (weight average).
There are essentially 3 types of monolignol monomers that can be Identified as monomer components of lignin, and they differ in the degree of their méthoxylation. They are p~coumaryi aioohoi, coniferyi alcohol and sinapyl alcohol. These lignols are incorporated In the lignin structure in the form of hydroxyphenyl (H)-, guaiaoyi and syringal (S) units. Naked-seeded plants (gymnosperms) such as pine trees contain mostly G units and low proportions of H units. Ail lignins contain small amounts of incomplète or modified rnonciignols. The primary function of lignins in plants is to lend them mechanical stability by cross-linking the vegetable polysaccharides. Lignin constitutes about 1/3 of the dry mass of wood, and according to rough estimates 30% of the non-fossil organic carbon mass on Earth, It is the third most abundant organic materia! after cellulose and Chitin, and Is thus a very readily available, renewable raw material for industrial products.
Lignin sulfonate is obtained as a by-product of paper manufacturing using the sulfite process. In this process, wood that has been reduced to wood chips is heated for about 7 to 16 hours in the presence of calcium hydrogen sulfite liquor and under pressure (for example δ to ? bar) and then the iigninsulfonio acid is removed fromThe lignoceilulose in the form of calcium lignin sulfonate in a washing and precipitation process. Liquors of magnesium, sodium or ammo-hjkjfTi sulfide can also be used instead of calcium hydrogen sulfite, and these produce the corresponding magnesium, sodium and ammoniurn salts of lignin-sulfonic acid.
When the washing: liquor1 is evaporated:, powdery lignin sulfonates remain. Annual worldwide production of lignin sulfonates is in the order of 51 million tons.
Sodium, calcium and magnesium lignin sulfonates are often used as the raw material for plasticising and liquefying concrete and mortar. Lignin sulfonates are also used as pelletising promoters in the kraft animai feed industry and as dispersing or compiexing agents In otherieids. in modern lubricating grease formulations, a not Inconsiderable proportion of the formulation cost is devoted toInhochemicaliy acting extreme pressure and anti-wear additlves {EP/A^: additive):, with the result that they often become the price drivers for lubricating: greases.
Many of these additives are produced In complicated, multistage synthesis processes, and their use is limited both in terms of the nature of the application and of their effective conoehiatidn in the final formulation due to the toxicological side effects that occur in many cases. In some applications, for example in constant velocity joint shafts or in slow running and heavily loaded rolling bearings, deficient lubrication conditions and/or contact between friction partners is unavoidable even when liquid additives are introduced:. Former practice in such cases was to use solid lubricants based on inorganic compounds (for example phosphate saits of calcium and zinc}, piasfe/powders (for example RTF!) or metal sulfides (for example M0S2L But these compoheilfs are also often expensive and can have a critical effect on the overall cost of a luhrlcant formulation.
Former practice in lubricating grease production was to introduce these additives in a second process step, performed eher the actual chemical reaction process of thickener formation. In this method, additives, particularly solid lubricants, must be distributed homogeneously throughout the relatively viscouslubricating grease by intensive mixing and sheafing processes with reiativeiy high mechanical effort in order to obtain their optimum effect. From a modern perspective, the following has often proven disadvantageous and prompted the present invention. lubricating greases containing sodium lignin sulfonates and sochum soaps or lithium soaps are already known from US 3239537 A, However, these are not suitable for use In lubricating constant velocity joint shafts, mainly because the grease attacks the TPE materials that are used m the bellows,
Usual lubricant additives and solid lubricants are normally based on nonrenewable raw materials and are often poorly biodegradable.
Furthermore: most common anti-wear additives and friction: reducing lubricant additives tentai expensive chemical synthesis processes: which represent a significant cost factor. Rarikmiariy when solid lubricants are used for heavily loaded friction : points, materials most frequently used are relatively expensive, for example MoS;:> or RIFE.
Object / advantage of the invention
The object of the invention Is therefore to avoid the drawbacks of the prior art as described in the preceding, and to make lignin sulfonates available in lobrioating greases both as cost-effective structure terming aganfs and as addibves to promote wear resistance, reduce friction and protect against ageing, and at the same imo to lend the lubricating greases good water resistance.
The presence of lignin sulfonate means that the use of other common lubricant additives and: solid lubricants: particularly MoSg, may be minimised or entirely dispensed with.
Summary of the invention
The invention is defined by the independent claims, Preferred variations repre-sent 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 precursor stage (base grease) is prepared by mixing at least - Base oil - Fatty adds and/or esters or salts thereof, wherein the fatty acid salt is at least partly a oalcium salt, for producing soaps and containing at least calcium soaps, - Organic and/or inorganic complexing agents if necessary, - .Alkaline earth hydroxides, wherein the alkaline earth hydroxides include at least: CaOH, - Water If necessary (for example as part of the hydroxides), and * Cadtgnin sulfonate haying average molecular weights (weight average) greater than 10000 g/mol. and heating to drive out components with tow being point when esters are used, and tu loitlate a! leas! one conversion of the alkaline earth hydroxide with the fatty acids and/or esters thereof and the lignin sulfonate, including reacting with the completing agents if compiexing agents capable of reacting with the alkaline earth hydroxides are used, foform a thickener structure in the base oil.
Components with low boiling point are those components that boil at temperatures up to about i00*C under normái pressure, such as water or C1~ to C4-alcohols.
In order to produce the base grease, the mixture is preferably heated: to temperatures above 120 *€, or preferably above 180 X. The conversion to base grease takes place In a heated' reactor, which may also be constructed as an autoclave or vacuum; reactor.
Then, in a second step the formation of IN thickener structure Is completed by cooling and any additional components such as additives and/or base ell are added to adjust to the desired consistency or the desired properties profile. The second step may be carried out In the same reactor as was used for the first step, but it is preferable if the base grease is fransferred from the reactor to a separate stirred tank reactor for cooling and 1er mixing in the additional components, if any.
If necessary, the lubricating grease: obtained in this way may be homogenised, filtered and/or deaerated.
Preferred substances are GaSJ-, Li/Ga- and: cafciumThiekened normal and complex soap greases to which calcium lignin sulfonate has already been added before the reaction phase to produce the base grease and is incorporated into theíluhhcatíni grease structure via a? thermal process in: such manner that It is present in highly homogeneous, oldnsoSuble form and results in high dropping point temperatures.
The use of alkaline earth salts, preferably calcium salts, for both the fatty acid salts and for the lignin sulfonate guarantees that salt metathesis does not take place either during the production of the base grease or during the application,
Salt metathesis, particularly with the salts of sodium:, must he prevented in: order to obtain a lubricating grease eenfeining lignin sulfonate with good water resistance and at the same time a high dropping temperature. For this reason, the use of sodium Igntn sulfonate and sodium hydroxide must be avoided. Water resistance is understood to mean that the grease is not emulsified by water and conforms to rating level 1-90 (test at 90 °C) in the test In accordance with DIN 51807-1 (version: 1979-9% Water resistance is further understood to mean that the grease conforms to rating level 1-80 (test at 80 ''€} in the test in accordance with DIN 51807-2 (version 1990-03).
The simultaneous application of an excess of alkali in the form of excess calcium hydroxide and possibly also calcium acetate or other calcium sails as the complexing agents is Intended to ensure that even small residual amounts of fi^éeüífoníé::apíii.0fop|j§ are neutralised in the lignin sulfohic acid and they lose their hygroscopic, water emulsifying and corrosion promoting action. A high process temperature, above 129 *0 and particularly above 180 °C also ensures that the residual moisture that sill remains in the lignin sulfonate is evaporated out of the reaction medium completely and any components of the lignin sui-fonate that have not been neutralised are neutralised by the calcium: hydroxide.
Standard lubricating oils that are liquid at room temperature are suitable for use m base oils. The base oil preferably has a kinematic viscosity from 29 to 2899 mnrP/s, particularly from 49 to 590 rnm2/s at 40 *C.
The base oils may be classified as mineral oils or synthetic oils, k/tineraf oils that are eligible for consideration include for example naphthene basic and kerosene basic mineral oils according to their classification in API Group I. Chemically modified low-aromatic and low-sulfur mineral oils with a small fraction of saturated compounds and better viscosity/temperature behaviour than Group I oils, ciasslfied as API Group II and ill are aiso suitable.
Regarding synthetic oils, polyethers, esters, poiyalphacleiins, potygiycols and alkyl aromatics and mixtures thereof are noteworthy, The polyether compound may contain free hydroxyl groups, but it may also be wholly etherised or terminal group esteriiied and/or It may ba produced from a starter compound having one or more hydroxy and/or oarbexyl groups |~C0ÖH}> Polypheny! ethers, whether alkylated or not, are also passible as the sole component, or better still as components of a mixture, Esters of an aromatic dh tri- or tetracarboxylic acid with one or more C2~ to G22 alcohols present in mixture, alcohols, esters of adipic acid, sebaOic acldrtnmethylolpropaPe, neopentyl glycol, pentaerythritol or clpentaerythnfol with aliphatic, branched or linear saturated or unsaturated C2 to €22 carboxylic acids, Cl 8 dimer add esters with €2 to C22 alcohols, complex asters, as single components or in any mixture thereof, are also suitable for use. soaos produced are either pure calcium soaps or mixtures containing calcium; soaps, besides calcium soaps particularly lithium soaps and/or aluminium soaps of one or more saturated or unsaturated monoparbexyiic acids having 10 to 32 carbon atoms, substituted or not, particularly having 12 to 22 carbon atoms, particularly preferably corresponding hydroxycarboxylic acids. Suitable carboxylic acids are for example lauric acid, myristic acid, palmitic acid, oleic acid, stearic add or behenic add and preferably 12-hydroxysteanc acid. Even corresponding low alcohol esters, such as corresponding triglycerides and the methyl-, ethyl-, propyl·, isopropyl- or sec,-butyl esters of acid/hydroxy acid, may be used with saponification instead of the free add group to achieve better dispersion.
The soap is converted into a complex soap by the presence of a complexina agent. The lubricating; grease compositions according to the invention contain- fcöap# f presence- of a complexing agent) have higher dropping points, for example higher than 200 °C (DIN ISO 2ffB|, Appropriate quantities fbr the addition of the Complexing agent are from Ö.S to 20 wt %, particularly 0.5 to 10 wt %.
The following complexing agents are advantageous for the purposes of the present invention. (a) alkali salt (preferably lithium sal) except sodium salt, alkaline earth salt (preferably calcium sat) or aluminium sali of a saturated or unsaturafed monocarboxylic acid, or also bydrexycarboxyläc acids having 2 to 8, particularly 2 to 4 carbon atoms, or a dicarboxyiie acid having 2 to 16, par-ticularly 2 to 12 carbon atoms, each of which may be substituted or un-substituted,: andfef {&} the alkalma and/or alkaline earth salt of hdfle acid and or phosphoric acid, particularly the products of Its reaction with ÜÖH' and/or Ca(OH)2.
Complexing agent (a) is preferably solely a calcium salt, particularly if this is used as calcium acetate to produce the base grease. Acetic add and propionic acid are pârfeulariy suitable for use as monocarboxylic acids. Nydroxybenzotc acids such as parahydroxybenzolc ácids salicylic acids, 2-hydroxy-4-hexylhenzpjo acid, metahydroxybenzolc seid; 2.5-dihydroxybenzoic acid (gen-lisle acid), :2,:6-dihyd:roxybe:nzoic: add (gamma-resoroyim acid) or 4-hydroxy~4-nietboxybenzoic acid are also suitable. Pameulady suitable dicarboxyiie acids are adipic acid sebacic acid (CteHiÄ), azelaic acid (CgH-isöz) and/or 3;-fert.-butyl-adipic acid (CicHigCV).
Possible substances for use as the borate (b) would include for example meta-borate, diborate, tetraborate or orthoborate, such as monolithium orthoborate or calcium orthoborate. The phosphates might be selected from alkaline (preferably lithium! and alkaline earth (preferably calcium) 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 add (e,g. aerosi!}, oil-soluble polymers (e.g„ pbipiefios, poiy{meth)acry!ates, polyisobutylenes, polybutenes or PS) or also di- and poly-ureas may also be used as co-thickeners. The bentonites, aluminosilicates, clap, silicic acid and/or olr-spluble polymers may be added to produce the base grease or Introduced as additives later, in the second step. The di- and poly-ureas rnay be introduced as additives.
The compounds according to the Invention may $ieo·contain other additives as additional substances. Common additional: substances for the purposes of the inversion are antioxidants, anti-wear agents, corrosion protection agents, detergents, dyes, lubrication enhancers, viscosity additives, friction reducers and high-pressure additives.
Examples of such would be: - Antioxidants such as amine compounds (e.g. aikylamines or 1-phenyl-aminonaphthaline), aromatic amines, e.g. phenyl-niphthyi amines or diphenyl amides, phenol compounds (e.g., lÉ~dMerPfeutyt-#~ methyipheno!}:, sulfur antioxidants, zinc dithiocarbamafe or zinc clithio-phosphato; - High-pressure additives such as organic chlorine compounds, sulfur, phosphorus or calcium derate, zinc dithiophosphate, organic bismuth compounds; » Substances designed to improve “oilinessÿ such as C2- to C6- polyols, fatty acids, fatty acid esters or animal nr vegetable oils; _ Anticorrosion agents such as petroleum sulfonate,: dinonyinaphthalerie sulfonate or sorbitan esters; ~ Atetsl deacivafors such as benzotrlezol or sodium nitrite; - Viscosity enhancers, such as polymethacryiate, polyisobeiylene, oigo-dec-1-ene, and polystyrenes; - Anti-wear additives and friction reducers such as organomoiybdenuro complexes (OMC), moiybdonum-divalkyl-dlfhiephdsphates, rnelybdenurh-dli-aikyl-dithiedarbamates: or molybdenum suifide-di-alkyl dithiocar-bamatos, particularly moiybdenum^dl-mfeutyf dliiipparbamafe and molybdenum disuiide-di-aiky! dithiocarhamafe (hbgßA(dialk$ oar-bamate}2 where m » Ö to 3 arid n «* 4 to 1}, - Friction reducers such as functional polymers, e.g. oleyl amides, organic polyether" ibi amide-based compounds, for example alkyl polyethylene glycol tetradecyiene glycol ether, |n addition, the lubricating grease compounds according to the invention also contain usual additives for protection agaméi, corrosion, oxidation and attack by metals, which function as chelating compounds, radlcai scaveo-qers, ÜV converters, reaction layer forming agents end the like.
Solid lubricants may be sei=ected for example from the group of polymer powders such as polyamides, polpmides or FIFE, graphie, metal oxides, heron nitride, metal: sulfides such as molybdenum sulfide, tungsten disulfide or sulfide mixtures «Ith tungsten, molybdenum, bismuth, tin and zinc base, im organic sets of alkali and alkaline earth metáls, Such as Calcium carbonate, sodium and : calcium phosphates. Solid lubricants may be divided into the following four groups: compounds with a lattice layer structure, such as molybdenum disulfide and tungsten disulfide1, graphite., hexagonal boron nitride and: certain metal halides; oxidio and hydroxicHc compounds of the transition and alkaline earth metals and carbonates or phosphates thereof; soft metals and/or plastics. The desired, advantageous lubricating properties may be adjusted with the use of lignin sulfonates with having to use solid lubricants. In many cases, solid lubrjoanfs may be omiited entirely, or at least significantly reduced, if said lubricants are used, graphite is the most favourable, lionln sulfonate may be chosen from: calcium lignin sulfonates have a molecular weight |Mw, weight average) greater than 10,000, particularly greater than 12,000 or even greater than 15,000 g/mol, for example from 10,000 up to 65,000 g/mol or 15,000 - 85,000 g/moi and particularly containing 2 to 12 wt %, particularly 4 to 10 wt %, sulfur (calculated as elemental sulfur) and/or I to 15 wt % particularly 8 to IS wt % calcium (calculated Ça), Besides, calcium lignin sulfonates, other alkaline earth lignin sulfonates may also be used, The average molecular weight (weight average) is determined for example by size exclusion chromatography, A suitable method? is the SEC--HÁLLS method as described In the article by: 65 Ë, Fredholm, S. Μ. Braaten end Bj, Christensen, ^Companion: of nioiebular weight and molecular weight distribution of softwood and hardwood lignosutfonates” published In '“Journal cl Wood Chemistry and Technology '. VbL 23:, No. 2, pages 197-218, 2ÖCB end the article ::yoiecular weight determination: of flgnb-sulfonates by size exduslen chromatography and multi-angle laser scstienng" by the same authors:, published In the Journal of Chromatography AT doiume :942, edition: 1-2, 4 January 2092, papes 191-199 (mobile phase:; Phosphate DldSO-SDi, stationary phase: Jordl-Cipkose-DVB m described in 2:.5). Suit-able calcium
Wgm sulfonates PP For example the commercially available: fxodkjcte INcsrtlp 11 ü anùBomrmtâÛ® 120 produced by iorrepuf LJgootscfe
The lubricating grease according to the invention is characterized by features of claim 14 and the lubricating grease, as applied In the process of the invention, by the preferred features of claim 6.
It was found that lignin sulfonates function as structure forming agents for water-resistant lubricating greases that also have properties as a solid lubricants or anti+wear additives and ageing stabilisers. At the same time, lignin sulfonate was observed to have surprisingly synergistic effects with other 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 aromaic; structures they contain*; their polymer structure and their low solubility In all types of lubricating oils, lignin sulfonates are suitable for use not only as a thicbener compo-nent but also as solid lubricants in lubricating greases and lubricating pastes. Their suffer content also enhances their EP/AW effect In the lubricating greases and the phenolic structures provide an age-inhibiting effect.
It is assumed that due to the large number ef polymer and polar aromatic units it contains., the lignin sulfonate structure is predcmlnanfly planar.
Accordingly, they are able to be deposited very well in layer sfruetures on metal surfaces under due to the effect of external frictional and shearing forces, because the ardrnafic nyelei of the lignin sulfonate enter into an associative reelp'· rocai action with the mota! surface, and metallic friction partners are separated from each othereffectively and permanently even under heavy loads and high pressures.
If calcium lignin sulfonate is added before the start: of the reaction phase during the production of soap thickeners, particularly ef calcium complex soaps, not only is to thickening effect soaps enhanced with: a high dropping point, but the anti-wear protection and lubrication effects of corresponding lubricating grease formulations are also enhanced, Conseguently, it is bénéficiai for the distribution and effect s! additives and solid lubricants if they are chemically or mechanically Incorporated in the thickener structure as an additional structurai element M situ during the reaction phase.
According to the prior art, it Is necessary in many cases to use specially treated, expensive fatty acids, such as 12~hydroxystearic acid, or special comptexlng agênfs such as borates or salts of acetic acid ; sehaclc acid and azsiafe acid to manufacture soap greases with high dropping points, yet these substances have little or no additional effect as anti-wear protection and friction reducing additives. If Ca-lignin sulfonates are included, the use of these other components may be reduced! significantly or even dispensed with altogether. The use of Ca-lignin sulfonates further offers the capability to formulate high-performance lubricating greases on the basis of renewable raw materials and abandon an additive-orientated chemistry that is detrimental to the environment,
If oils consisting of unmodified or easily modified native fatty acid esters are thickened using metal soaps based on animal or vegetable fatty acids, and if . lignin sulfonates are used as the only additional thickening agent and at the same time the only additive component, lubricating greases are obtained that have been produced almost exclusively on the basis of renewable raw materials, the only exception being calcium hydroxide used for the metal soaps.
These greases protect against ageing and wear, and have the effect of raising the seizure load and lowering friction when lignin sulfonates are included as a thickener component.
The lubricating greases according to the invention are parley lady suitable lor use in or for constant velocity joint shafts, rolling bearings and gearboxes. li the base oils used consist of readily biodegradable esters, such as those that contain mostly renewable raw materials, the lubricating greases are also su it-able for total loss lubrication In the environmentally sensitive area (for example in mining or agriculture).
In the special case of lubrication for mainteplhee-freé constant velocity joint shafts, the first lubncating grease has been formulated using calcium lignin sub fonalé that differs from the prior art In that it assures ÄC! operating Hie and good levels of efficiency entirely without the use of M0S2 and other organic and inorganic molybdenum compounds.
The absence of ether additives also serves to lower the friction bbeílcísnt, profod against seizure load and wear and renders the product highly compatible with the materials used in standard commercial constant velocity joint shaft bellows, such as chiefoprShe robber and thermoplastic polyether esters. Since the sulfur contained In lignin sulfonate Is bound by thermally stable sulfonate groups, unlike tlii;#: additives it is only released at very high temperatures andforwiii very high levels of activation energies, such as do not occur in lubricating grease applications except with tribocontacts under very high loads, in this way, suhseguenf vulcanisation or crossiinking of rubber materials by the sulfur released from ageing lubricant is largely prevented.
If calcium lignin sulfonate Is used in a lubricating grease formulation that has been adjusted with excess ealeiernhydroxide to be overbasic, this prevents free lignin suifonic acid from having a hydrolytic effect on materials used in the bellows, such as thermoplastic poJyether esters. A special aspect of the present invention is that It may be used to obtain cost-optimised lubncating grease formulations for lubricating points that are under heavy load, such as In constant velocity joints in particular, and that are well compatible with bellows containing; for example, thermoplastic polyether esters (TPE) and chloroprenes (CR), while offering a high degree of efficiency, low wear and a long service life.
Example A (comparison example): 958 9 tallow fatty acid, 958 g bosf:tailow:,: 95&^g calcium acetate, 20 g frise-dium phosphate, 27.7 g calcium horale and 358 g calcium: hydroxide were placed in a reactor in 12,000 g of a base oil mixture and 180 mi water was added. 1¾ pasa was heated to 198 °C in a defined temperature programme while stirring so that the added water and the reaction water 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 adding 3700 g of the base oil mixture, the final product was homogenised in a toothed colloid mill . The grease obtained thereby is suitable for use as constant velocity iolnf; shaft grease.; 1er example. ; Example B: 480 g taiiow fatty acid, 445 g beef tallow, 488 g calcium acetate* 27,7 g trisodium phosphate,; 27.? g calcium boraié and 188 g oaicium hydroxide and 920 g calcium lignin sulfonate (Noriig 110 powder manufactured by Éotragard ygnotech) were placed Ip a reactor in 14,008 g of a base oil mixture and 158 ml i water was added. This base was heated to 208 '::C in a defined temperature programme while stirring so that: the added water and the reaction water evaporated, Additives (see table) were added to the base at certain temperatures due ing the cooling phase. After the base was adjusted to the desired consistency by adding 3450 g of the base oil mixture, the final product was homogenised in : a toothed colloid mill, The grease obtained thereby is suitable for use as con stant yelpeity joint shaft grease, for example.
Example € fcpmparlsen example): 809 § 12~hydroxy stearic acid, 288 g sebacic acid, 388 g calcium acetate and : ' 15?,3g calcium hydroxide were placed in a reactor in 5800 g of a base oil mho· tore, 84 g Li ON x hLO was dissolved in 250 ml wafer and added. This base was heated to 200 °C in a defined temperature programme while stirring so that the added water and the reaction water evaporated. Additives were added to the base at certain temperatures during the cpollng phase.
Alter the base was adjusted to the desired consistency fey adding 3118 g. of the base ail mixture, the final product was homogenised in a toothed colloid mil The grease obtained thereby is suitable for use as rolling bearing grease, for example.
Example Ö; BQQ g 124tydroxy stearic add, 216 g: sebacie acid, » g caiolum acetate; and 720 g calcium hydroxide and 3(K) g calcium lignin sulfonate (Móriig 11D powder manufactured by Borregard Ugnotech) were placed in a reactor in 5000 g of a base oil mixture. 48 g UOH x H;;0 ;^as dlaseked in J6b ml water and added. This base was heated to 200 "C In a defined temperature programme while stirring so that the added pater and the reaction water evaporated. Additives were added to the base at certain temperatures during the cooling phase.
After the base was adjusted to the desired consistency by adding 3118 g of the base oil mixture, the final product was homogenised m a toothed eolloM mi. The grease obtained thereby is suitable for use as rolling bearing grease, for example. 1380 g tallow fatly acid, 1360 g beef tallow, 80 § trisoÉum phosphate, 30 g calcium borate. 1400 g calcium acetate and 493 g calcium hydroxide were placed in a reactor in 12,000 g of a base oil mixture: and 150 ml water was added. This base was heated to 230 *C in a defined temperature programme while stirring so that the added water and the reaction water 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 adding: 3125 g of fie base oil mixture, the final product was homogenised in a toothed colloid mill.
The grease obtained thereby is suitable for use as rolling bearing; grease, for example.
Example F: 1280 g tallow fatty add, 1240 g beef tallow, 80 g trisodium phosphate. 80 g calcium borate, 1278 g calcsum acetate, 493 g calcium hydroxide and 835 g calcium lignin sulfonate (Norläg 11D Powder manufactured by Borregard ygnote#h| were placed in a reactor in 12,000 g of a base all mixture and 150 ml water was added. this tease was healed to 225 *C m a defined temperature programme while stir-ring so that the added water and the reaction water:evaporated. Additives were added id tie base at Pertain temperatures during the cooling phase. After the hasd was adjusted to the desired consistency by adding 3125 g of the base ol!: mixture, the final product was homogenised in a toothed colloid mi. The grease obtained thereby is suitable for use as rolling bearings grease, for example:. 975 g caiciunv12 hydroxy stearate, 2|;5 § OalPium acetate and li p calcium borate were placed in a reactor in 3500 g methyl oieate ester, This base was heated to 200 X so a defined temperature programme 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 adding; Th©: g methyl oieate ester, the final product was homogenised in a 3-rolier mil. The lubricating grease obtained thereby is made on the basis of predominantly renewable raw materials. 841 g: calcium 12-hydroxy stearate, 219.5 g calcium acetate, 15 g calcium borate and 418 g calcium lignin sulfonate (Noriig 11D Powder manufactured by iorregard ygnoteeh):were placed In a reactor in 1965 g methyl oieate ester. This base was heated to 200 X in a defined temperature programme 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 adding 1684 g trimethyfolpropane trioleate ester, the final product was homogenised in a 3-roller rniib The lubricating grease obtained thereby is made on the basis of predominantly renewable raw materials.
Examples 1 and 3:
The products of example formulations I and: j are similar to the production of example H but with the use of different quantities of calcs uro~12 hydroxy stearate* calcium acetate and calcium lignin sulfonate1 and difieredi compositions of ester base oils. The lubricating greases obtained: thereby are made on the basis of predominantly renewable raw materials.
Table 1.: Joint shaft grease formulations
Example A B
Reference Invention calcium corn-
Descriptfon pfox calcium complex with S% lignin with MoS2 sulfonate: 1, Thickener: 1/1 Lignin sulfonate:
Calcium lignin sulfonate (),0 foi 1.2 Fatty addsMnglycerktes:
Mixed fatty acsds 4 8 2.9
Mixed triglycerides 4,8 2.8 1.3 Alkali hydroxide:
Ca(OH)2 1.8 1.5 1.4 Compiextng agent;
Ca acetate 4.8 3.0
Ca borate 0.1 0 2 2. Base oils:
Mixed basic minerai oil (at v40~ 100mm4/s) 79.6 80,8 3, Additives:
Ant-oxidant 1 0.8 0.S
Antioxidant 2 0.8 8,5
Corrosion protection 0.5 (),2
Solid lubricant, graphite 0.6 1,0
Solid lubricant, MoS2 1,8 8.0
Totai 100 100 4. Characteristics Method Unit 4.1 General physical data
Penetration unworked DIN ISO 213? 0:.1 mm 383 315
Penetration worked 60-doable nyeles DIN ISO 213? 0.1mm 351 340
Copper corrosion 240 /100 X DIN 51811 Evaluation level 1-108 1-100
Dropping point OIN ISO 2176 X- 240 280
Oil separation 18 h/48 X DiN 51817 % 0,4 2.1
Oil separation 7 4(40 X DIN 61817 % 2 8.0 4.2 Water resistance
Static water resistance 3 h/90 X DIN 51807-1 Evatetion level 1-98 1-90
Washout ioss at 80 X DiN 51807-2 Evaluation level 1 1 labte 1 (continued): Joint shaft grease fonnuiaitens
Example â P
Reference Invention calcium
Description complex catesum complex with 6% iignm sal-with MoS2 fonate 4.3 Friction reduction SRV at 80 °C (40 Ha. 1.5 Ampiiud®, $PN: load) ASTfvf D D5 707-05
Friction coëiicteni 0.10? 0,007
Process steady steady SRV at 1 SO *C (4014¾1,5mm Amplitude. 500N: load) ASM D: 05707-05
Faction coefficient 0.007 0.035
Process steady steady 4.4 Anti-wear protection
VKAweidtead PIN 51350-4 N 3400 3800 N VKA calotte 1O00N/1 min DiN SF35Ö-5 mm 1.02 0.62 4.5 Compatibility wlh oellbws materials
4.0. 1 Chloroprene Ιη&ρ$&4Ρ2188 iV128*C -Shore A DIN 53505 ,-2 .1 'Volume change DIN 53521 '% +3,5 -0.5; -Change in tensile strength DIN 53504 % -0:8 -1,2: -Chaitge in elongation DIN 53504 %. -22.1 -ig 4.0. 2 NBR rubber SRE NBR 34 7d/100 SD DiN 53538-3 -Shore A DiN 535(55 -2 -3 -Volume change DiN 63521 % ·*&4· + 3.7 -Change in tensile strength DiN 53504 % -2.8 - o •Change in elongate DIN 53504 % -7,8 -4,5 4.6.3 ΤΡΞ elastomer Hytrei 8332:3361/126¾ -Shore D DIN 53505 -3 ~2 -Volume change DIN 53521 % +13.1 + g.2 -Change in tensile strength DIN: 53504 % -32.8 f 5.7 -Change in elongation DIN 58504 % -27 * #1
Amitel EB 463 336h/125 *C
•Shore O DIN 5350-5 -g Q •Volume change DIN S8Ő21 % +10,7 +10.2
-Change so tensile strength 08453504 % -1::5 ~i$J -Change in elongation PIN: 53504 % -io * y,& 4.6.4 EPDM rubber Vamso V78HR SOOiVI^O *© -Shore A DIN 53505 +3 + 5 -Volume change DiN 53521 % +S + 8 3 -Change in tensile strength DiN 53504 % 47,4 .^.8 -Change in elongation: DiN 53504 % -30 - 35 5, Service Fie testen ·|Ιιο constant velocity joint shaft
Service; pie Overroilings (mill ) 13.6 11,2
Average: sfeadSAsteteiemperatyre: !iC 41.1 3§§
Table 2: Röiiim? tearing grease formulations
Example COE F
Reference invention Reference invention
Caicsum/bf hiurn Oaícitfm/UtNum Caicium/Uthium öasedpflgn complex complex Calcium Complex complex with 6% lignin with 5% lignin sulfonate sulfonate 1. Thickener: t,1 Lignin sulfonate:
Calcium lignin sulfonate 0.0 6.0 6 5.1 1.2 fatty acid s/4ri g ty ceri d es ; 12-HSA 8,0 5.0
Mixed falty acids 8.9 3.8
Mixed teglycerides 6.8 8.4 1.3 Alkali hydroxide:
LiOH'H2G 0.6 0,4
Ca{OH)2 1.6 1.0 2,§ 2.0 1.4 Gompiexlng agent:
Sebacic aesd 2,9 1.8
Cs acetate 3.0 2.4 7.0 5.7
Ca borate 0.4 0.3 2. Base oils:
Mixed basic mineral oil (at v40~ 100 »%) 81.6 62.0 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): foiling bearing grease formait4lohs
Example CD E F
Reference Invention Reference Invention
Calcium/Uthiura Caieiam/Lithium Calclum/Uthium
Description complex complex Calcium Complex: complex with 6% I ignln with δ% I Ig ni n sulfonate sulfonate 4. C hereof eristics Method Unit 4.1 General physical data
Penetration unworked DIN ISO 2137 0.1 mm 2§9 270 199 199
Penetration worked. 60 double cycles DIM ISO 2137 0.1 mm 310 299 234 232
Dropping point DIM ISO 2176 "C 296 230 2§§ >260
Oil separation 18-0/40 "C DIN 51817 % 2.2 1.1 0 Ö
Oil separation 7 d/40 °C DIN 51817 % 4.1 3,9 9.6 0.6 4.2 Water resistance
Static water resistance 3: h/SO “C DIN 61307-1 Evaluation level 1-90 1-90 T-9Q 1-90
Washout loss at 80 ”C DIN 51807-2 Evaluation level 1 1 1 1 4.3 Corrasion protection
Emcor distillée! water DIN 51862 Evaluation lével 0-0 0-0 0-0 0-0 4.S Anti-wear protection efficiency VKA weld load PIN 51360-4 N 2QÖÖ 3400 2000 3200 VKA calotte 1ÛGÔN/1 min DIN 51350-5 9.1 mm 0,91 0,45 0,89 9.67 5. Rolling bearing tests FAG-FE9 (An 500/6000/120 *C) DÍN51821-2
Average operating life LID 78 11® 35 78
Average operating life ISO 115 220 74 T56 :
Table 3; Lubricating gréas©formuls'd&n with bas© oils from renewable raw materials
Example G H ? J
Reference invention Invention invention
Cefeium Com- Ceieium
Description piex Calcium Complex Cssfcium Complex Complex 1, Thickener: 1-,1 Lignin sulfonate;
Calcium lignin sulfonate 0 7.1 8,9 5,1 1,2 Finished soaps;
Os^l 2 hydroxy stearate 19.5 14,1 13 8 10.1 1,6 Completing agent:
Ca acetate 4.6 2.9 4,8 2.1 Cä berate 0.3 3.2 0.3 0.1 2, Bas© oils:
Trimcthyioi propane trioleate 28.5
Methyl oieato 73.6 73.6 63,9 52.1 3, Additives:
Antioxidant 0.1 0.1 0.1 0.1
Corrosion protection 2 2.0 2.-0 2,0
Total ' 100 100 100 100 4, Characteristics Method Unit 4.1 General physical data
Penetration unworked DIN ISO 2137 0.1 mm 183 163 176 232
Penetration worked, 60 double cycles DIN ISO 2137 0.1mm 221 209 219 301
Copper corrosion 24h /100 "C DSN 51811 Evaluation level 1-108 1-100 1-180 1-100
Dropping point DIN ISO 2176 aC 210 250 248 205
Oil separation 186/40 "C DIN 51617 % 0.4 0.0 0.0 0.4
Oil separation 7d/40 *C DSN 51817 % Q,$ 0.5 0.1 2 8 4.2 Water resistance
Static water resistance 3h/§0 *C DIN 51807-1 Evaluation level 1-80 1-90 1-90 1-98 4.3 Corrosion protection
Erncor distilled water DIN 51602 Evaluation level 1-1 1-1 1-1 1-1 4,5 Anti-wear protection VKA weld load DIN 51350-4 H 2000 2800 3008 2400 YKA calotte 1808N/1. min DIN 51350-5 0,1 mm 0.83 0 67 0.54 8.48

Claims (6)

Az EP 2 531 51? lajstrom számit ay répái szabadalom Igénypontjainak magyar fordításaiEP 2 531 51? Hungarian Register of Hungarian Carrots 1, Epris igninszuiíonáíoi tartalmazó kenőzsírok ejellítására, amely magában foglalja a) a következők összehozásának: - legalább egy aíapolaj, - legalább egy telített vagy telítetlen, 1®~32 szénatomos, adott esetben belyettesltetí mormkarbonsav-kaleíum-szappan. - legalább egy komptexloépző szer, amelyet a következők közöl választunk: |í| telített vagy telítetlen, 2-8 szenatomes monokarbonsav vagy hklroxíkarbonssv, 2-16 szénatomos díkarbonsav alkálisója, a rfátriumsó kivételével, aikaÄölBmsöja vagy aiumíniumsőja, amely savak mindegyike adott esetben helyettesített, p| bórsav- és vagy föbzíörsav átkaik és/vagy alkáliíöldíémsója, beleértve azok tíöH-val és/vagy GaCÖHl^vel alkotott reakoiötermékit, (|i|| ezek keveréke, és - legalább égy kaíciumdígninszolíbnát, amelynek tömeg szerinti átlagos molekulatömege 10 Ő0ö g/mdEnál nagyobb, makóié kiváltására és az alacsony forrásponté komponensek eltávolítására 120 X-náí magasabb hőmérsékletre való melegítésének lépését egy alapzsir előállítására, és b) a lehűtés és aíapoíaj és adott esetben adalékanyagok keverés közbeni hozzáadásának lépését,1, comprising: a) at least one oil of at least one saturated or unsaturated, C 1 -C 32 carbon atoms optionally substituted by morpholecarboxylic acid. - at least one complexing agent selected from: | í | saturated or unsaturated, 2-8 senatome monocarboxylic acid or hcloxy carboxylic acid, alkali salt of C2-C16 carbocarboxylic acid, except for the sodium salt, timothyBium, or aluminum salt, each of which is optionally substituted, p | boric acid and / or boric acid and / or alkali metal salt thereof, including their products of formula (I) and / or GaCÖHl ^, (i.e. a mixture thereof, and at least four potassium dinolinol sols having a weight average molecular weight greater than 10 µg g / mdE) , a step of heating a macaw to remove low boiling components to a temperature of 120 X, to produce a base fat; and b) a step of adding cooling and boiling water and optionally additives during mixing; 2, Az1, Igénypont szerinti eljárás, azzal jellemezve:, hogy az a) lépésben kalcium-hldirökldot adagolunk adott esetben további alkálltildflm-bidmxldok: mellett. 3» Az f, Igénypont szerinti eljárás, azzal jellemezve, hogy a kenőzsírt bázíkussá tesszük, különösen íaíéSíégben vett kaícíum-hitíroxid hozzáadásával,Process according to claim 1, characterized in that, in step a), a calcium masterbatch is optionally added in addition to the additional bridging flm. 3, The process of claim f, wherein the lubricating grease is made basic, in particular by the addition of caustic soda hydroxide, 4, Az 1 igénypont szerinti eprás, azzal jellemezve, hogy a melegítést 180 "C-nál magasabb hőmérsékleten végezzük. 5v Az 1. Igénypónt szerinti eljárás, azzal jellemezve, hogy az a) lépésben kalcium-hidroxki mellei lltium-bldroxidoi magnézlunvhidro.xídot és/vagy alumínium-híároxldot, illetve aíumínium-áíkoholátokat és/vagy alumíniuni-oxoalkoholátokat és/vagy telített vagy telítetlen, adott esetben helyettesített 10-32 szénatomos monokarbonsavak lítium-·, magnézium-- és/vagy aíundníum-szappanjalt is adagoljuk, t»4te 1. igénypont szerinti eprás, azzal jellemezve, hogy a kebőzs# tartalmaz, egymástól függetlenül: - 55 - 82 tomeg% különösen 70 - 86 tőmeg% alapoíajat, - ö - 40 tömegé, különösen 2~ 10 lomegSá adalékanyagok * 3 - 40 tömeg%, különösen 6 - 20 tomeg% kalcium-szappant és - 0;5 -10 tömeg% komplexképZÖ szed, és - adott esetben feleslegben vett Ca(GB)rt előnyösen ö,01 - 2 iörneg%-ban, és - Cl ,5 -1#{$$£$&«NtMiHönöépt4 » 8 tomeg% kaíciumdigoinszülfonátöt adott esefhon további alkálltöldfém-'lignlnszyttdnátok mellett mindegyik eset bon a teljes kenőzsinkompazielöra vonatkozatva. Ί, Az 1, Igénypont szerinti eljárás, azzal jellemezve, hogy az alapzslrt az a) lépésben eiöilliha|uk a következők alkalmazásával: » 4i * ?0 tomeg°4, különösen 45 - 60iömeg% alapdiej* -10 - 60 tömeg%, különösen 15 - 50 tömeg% kalcium-szappan és - 5 - 30 tömeg% komplexképző szer, és - adott esetben feleslegben vett Gá(ÖI%. előnyösen 0.02 - 4 tömeg% mennyiségben és - 0,7 ~ 30 fömeg% kalclunr-llgnínszulíonát, ádött esetben további alkállfoldfém-tlgnl nezulfoneto k mellett:, mindegyik esetben az alapzsír-kompozícióra vonatkoztatva.4, according to claim 1, characterized in that the heating is carried out at a temperature of more than 180 ° C. 5v The process according to claim 1, characterized in that in step a) calcium hydroxide is a calcium hydroxide and magnesium hydroxide. / or aluminum hydroxide or aluminum alcoholates and / or aluminum oxoalcoholates and / or saturated or unsaturated monocarboxylic acids, optionally substituted with 10-32 carbon atoms, lithium, magnesium and / or aliphatic soaps are added, i.e. Cassette according to claim 1, characterized in that the crust # comprises, independently of each other: - from 55 to 82% by weight, in particular from 70 to 86% by weight of base weight; , especially 6 to 20% by weight of calcium soap and 0 to 5 to 10% by weight of complex complex, and optionally excess Ca (GB) rt is preferably 1, 2 to 2% by weight, and - Cl to 5 - 1 $$ {# £ $ & Besides further alkálltöldfém-bon vonatkozatva'lignlnszyttdnátok each case the entire kenőzsinkompazielöra NtMiHönöépt4> 8 wt% kaíciumdigoinszülfonátöt optionally esefhon. The method according to claim 1, characterized in that the base grate in step (a) is predominantly utilized in the following manner: 4i * 0 0%, in particular 45% to 60% by weight base base 10 to 60% by weight, especially 15 to 50% by weight of calcium soap and 5 to 30% by weight of complexing agent and, optionally, an excess of Ga (ÖI%, preferably 0.02 to 4% by weight, and 0.7 to 30% by weight of calcium chloride; in each case with additional alkali metal metal, in each case, relative to the base fat composition. 8. Az 1. vagy 4, igénypont szerinti eljárás, azzal jellemezve, hogy a kenőzsír tartalmaz egymástöí tüggetienül 0,2 ~ 5 tőmeg% graltpt és/vagy nem; tartalmaz szilárd kenőanyagot vagy 1 tömeg%~nál kevesebb szilárd kenőanyagot tartalmaz, különösen nem tartalmaz fv1o$rt.Process according to claim 1 or 4, characterized in that the lubricating grease comprises at least 0.2 to 5% by weight of graltpt and / or not; contains a solid lubricant or less than 1% by weight of solid lubricant, and in particular does not contain fv1o $ rt. 8. Az 1 . Igénypont szerinti eljárás, azzal jeiiemezvo:, bogy a kalcium-szappant in situ -éltjük elő kalcium-hidroxid és olyan telített vagy telítetlen, 10-32 szénatomos, különösen 16-20 szénatomos mono karbonsav reakeíőfermékekéni amely sav adott esetben helyettesített, például bkiroxicsoporttaí, mint észter vagy anhídrkt8. Process according to claim 1, characterized in that the calcium soap is produced in situ by calcium hydroxide and saturated or unsaturated C 10 -C 32, especially C 16 -C 20 mono-carboxylic acid reaction products, optionally substituted, e.g. ester or anhydride 10. Az 1. igénypont szerinti eljárás, azzal jellemezve, hogy a kompíexképző szert az a) lépégen egy kaiciumsó, különösén kalcium-Ndroxid, és telített vagy telítetlen, 2-6 szénatomos, különösen 2~4 szénatomos monokarbonsav vagy 2-18 szénatomos, különösen 2-12 szénatomos dlkarbonsav reakolőtérmekéként adagijuk, amely savak oiindegyile adott esetben helyettesített,, például hidroxícsoportíai, mint észter vagy anhídrieh10. The method of claim 1, wherein the complexing agent at step a) is a calcium salt, in particular calcium Ndroxide, and saturated or unsaturated, C2-C6, in particular 2 to 4 carbon atoms, or C2 to C18, in particular as a reaction space of dccarboxylic acid having from 2 to 12 carbon atoms, optionally substituted with alkyl, for example hydroxy, as ester or anhydride 11. Az: 1, Igébpónt szerinti eljárás, azzal jellemezve, hegy á komplexképzo szer egy karbonsavxkilóiümsó, és ín situ állítjuk elő az a} lépésbea tellett vagy tetlétton, .¾ különösért 2-4 szénatomos monokarbonsav vagy 2*1 Öj különösén 2-12 szénatomon dlkarbonsav adagolásával, amely savak mindegyike adott esetben helyettesített:, például hidroxlcsoporttai, mint észter vagy anhldrld. 12« Az:1-11 « igénypontok legalább egyike szerinti eljárás, azzal jellemezve:, hogy a kaioiuni-iigninszuifonatoi hozzáadás előtt vízmentesíf ük ös§ tömeg%-náü kisebb víztartalomig, például a bázisolajban yaté hevítéssel 95 “Ónál magasabb, különösen 100 ;:C-náí magasabb, például 120 iVC hőmérsékleteid 13« Az, 1-12,. Igénypontok legalább egyike szerinti eljárás, azzal jellemezve, hogy a kompozíció tartalmaz kompiexéképzö szereket 0,5 ~ i0 tomeg% mennyiségben, 14 Kenözeír*kempozsció, amely tartalmaz - Sí - 82 tömeg%s különösen 70 » 85 tomeg% méinyiségben alapolajat, ~ (I - 40 iömeg%, különösen 2 -10 törneg% mennyiségben adalékanyagokat, - 3 ·· 40 iömeg%, különösen 5 - 20 tőmeg% mennyiségben telített vagy telítetlen, 10-· 32 szénatomot,: adott esetben helyettesített monokarbonsav-kaleinm-szappanofcai, - 0,5 -10 tomeg% mennyiségben komplexképző szereket, amelyeket a kővetkezők közűi választunk: (t) telített vagy telítetlen, 2-8 szénatomos monokarbonsav vagy hídroxikarbönsav, 2-16 szénatomos dikarbonsav alkálísója, a nátriumsó kivételével, alkálíföldfémsója vagy alumíniumsója, amely savak mindegyike adott esetben helyettesített, (II) bérsav és/vagy foszfersav akáíl- és/vagy alkáliföldfémséja, beleértve azok yObl-vaí éSitVigy Ca(ÖH)rvel, adott esetben feleslegben vett, előnyösen 0,01 - 2 tömeg% Ca(OH)2~vel képezett reakciótefmékét, és (ül) ezek keveréke,, és ~ 0,5 ~ 15 tömeg%, és különösen előnyösen 2-8 tömeg% mennyiéiben kalcium-íignínszulfdnátoí, adott esetben további alkáliföldfém-lígnínszullönátok melleit, mindegyik esetben a kenőzsír teljes kompozíciójára vonatkoztatva, ahol a kompozíció küppenetráclé értéke (Walkpenetration} 265-385 mm/10 25 °C~on az ISO 2137 szerint meghatározva. 15, A 14. igénypont szerinti kompozíció, azzal jellemezve, begy a kompozíció kúppenelfácío értéke (Waíkpenetraíion) 285-355 mm/10 az ISO 213? szerint meghatározva. 15, A 14, vagy 15. igénypontok legalább egyike szerinti kompozíció, azzal Jellemezve, Hogy az alspöíaj kinematikus viszkozitása M - 2505 mm^eo, előnyösen: 40 - 500 mm'Vsec 40 cC-on. fik A 1:4-15, igénypontok legalább egyike szerinti kompozíció:, azzal jéíiernezve, begy a kömptexképző szer a következekből áll: · 2-8 szénalomos, különösen 2-4 szénatomos teiitett vagy telítetlen monokarbonsav, vagy 2-16, különösen 2-12 szénatomos dikarbonsav alkáilsója, előnyösen titlumsója, atkáíiföldférasöfa. előnyösen kalcíumsoja, vagy aiuminiumsója, amely savak mindegyike adott esetben hefyétfesííett 1#, A 14-17 Igénypontok legalább egyike szerint; kompozíció, azzal jellemezve, Hogy az adalék tartalmaz a kővetkező csoportból választott egy vagy több tagot: - amtnvegyilefek, fen:ôlvegybletek;pl^ntarmlmâ antlozldánsok, clnk-ditíokarbamát vagy olnfeditietoszfat mint aniioxidánsok; - szerves kiórvagyületek, kén, foszfor vagy kalcium-borát cink-difiofoszfái, szerves bizotujveiyöletek mint nagynyomás adalékanyagok (Hochdmckedditive); - C|~ǧ f okolok, zsírsavak, zskoav-észterek vagy áilai vagy növényi olajok; - petroleum-szuifonát dinoniínaítalinszulíonát vagy szorbitán-észterek mint korrőziógátlő szerek; - benzotríazol vagy nátdum-níírít mint fém-deaktívátorok; - polimetakítib poliízobutllén, oÍígo-doo-1 -én és poilszfiroiok mint víszkozitásíavitók; - molibdérvdíaíkil-dltiokarbamát vagy rnollbdén-szulfíd-'dialkil-'ditíükarbamát vagy aromás aminok mint kopásgáfíó adalékanyagok, - funkciós polimerek, így például oieiamldok, szerves poíiéter- és amid-aiapú vegyületek vagy molibdén-ditiokarbarnat mint sorlödáscsokkentők (Friction Modifier); és ·· poiimer porok, így például poiiamidok, poíiímidek vagy PfW, grafit, lém-oxldok, bór-nitrid, fémnszutfidek, így például moiíbdén-diszuifid, woííram-diszuiíid vagy wolfram-, mofibdén-, bizmut-, orv és cink-alapú kevert szulfidok, alkáli- és aiálioldfcek szervetlen sói, így például kalcium-karbonát, nátrium- és kalcium-foszfátok mint szilárd kenőanyagok. 19. A 14·Ί8. igénypontok legalább egyike szerinti fompoziciö, asai jellemezve, hogy a kenőzsír vízálló, éspedig a) az 1-SO értékelési szakasz DIN 51807-1 teszttel ossszbangbarvvégzeti vizsgálata éslvagy b) az 1-80 értékelési szakasz DIM Sí887-2 teszlet összhangban végzett vizsgálata szorint. 2#, A 14-lt. igénypontok léplibb egyike szerinti kömpozfciö, azzá! jeíiérőézvé, hogy a kaloinm-iigninszujfonát tömeg szerinti átlagos molekulatömege (ÍV!w? weight average) 10:080 g/mol-nái nagyobb, különösen 12 OÖI gímöbnál nagyobb vagy még 15 808 g/mol-nál is nagyobb, amely ettől függetlenül tartalmaz 2 - $2" tömég%s különösen 4 -10 törneg% kenet (elemi kénként számrtva) IsAragy szintén függatlénü! tartalmaz 5-15 torneg%, különösen 8 -15 tÖmeg% kalciumot, 21. A 14-20. igénypontok figaiiöb egyUteipiAiItonpezfelé, azzal!Jellemezve, hogy a kenőzsír tartalmaz olyan alapolajai amély utántermelödo fnachwaohsende) nyersanyagokon alapul és/vagy amely Oö-néi nagyobb %-baouMntermeiődő nyersanyagokbói készet - 22. A 14-20. igénypontok legalább egyike szerinti kompozíció, azzal jellemezve, hogy a kompozíció eseppenéspohfa a DIM ISO 2178 szerint meghatározva 280 °€ feletti. 28. A14-22. igénypontok legalább egyike szerinti kompozíció alkalmazása legalább egy hajtómű kenésére. 24. A 14-22 igénypontok legalább egyike szerinti kompozfejé alkalmazása redőzött csukíósfengelyiok anyagként höre lágyuló poiíéterészterekhől elöiitott redőzött üsuklóstengely tokkal ellátott szinkron forgó tengelycsuklókban a konŐhdpk kenésére.11. The method according to claim 1, wherein the complexing agent is a carboxylic acid silicone, and is produced in situ by step a or at or, especially, from 2 to 4 carbon monocarboxylic acids or 2 * 1 to 2 to 12 specifically. carbon atoms by the addition of dicarboxylic acids, each of which is optionally substituted with, for example, hydroxy, as an ester or anhldrld. Method according to at least one of claims 1 to 11, characterized in that, prior to the addition of quinolignin sulfonate, an anhydrous content of less than §% by weight of water, for example by heating with base oil in the base oil of 95 Ó, is higher than 100, in particular 100; C higher than, for example, 120 iVC 13 «Az, 1-12 ,. Process according to at least one of the claims, characterized in that the composition comprises complexing agents in an amount of 0.5% by weight, 14 Kenoyz * camping, which comprises - from about 70% to about 70% by weight of base oil, (I) - 40% by weight, in particular from 2 to 10% by weight of additives, - 3 · by 40% by weight, in particular from 5 to 20% by weight of saturated or unsaturated, 10 to 32 carbon atoms: optionally substituted monocarboxylic acid kalein mate soap, 0.5 to 10% by weight of complexing agents selected from the group consisting of: (t) a saturated or unsaturated, C2-C8 monocarboxylic acid or hydroxycarboxylic acid, an alkali metal salt or an aluminum salt thereof, with the exception of the sodium salt, except for the sodium salt; optionally substituted (II) whey and / or alkaline earth metal salts of phosphoric acid and / or phosphoric acid, including yObl-ys. such as Ca (HH), optionally with excess, preferably from 0.01 to 2%, by weight of Ca (OH) 2, and (sit) a mixture thereof, and? 0.5 ~ 15% by weight, and in particular preferably 2 to 8% by weight of calcium sulfonate sulfate, optionally additional alkaline earth metal liquor bellies, in each case with respect to the total composition of the lubricating grease, wherein the composition has a crystal leachate (Walkpenetration} 265-385 mm / 10 at 25 ° C according to ISO 2137) determined. A composition according to claim 14, characterized in that the composition has a tapered adhesion value (Waqpenetraion) of 285-355 mm / 10 of ISO 213? determined according to. Composition according to at least one of Claims 14 or 15, characterized in that the kinematic viscosity of the subspecies is M - 2505 mm e eo, preferably 40 - 500 mm ′ Vsec at 40 cC. Composition according to at least one of claims 1 to 4 to 15, wherein, as defined herein, the coagulant is composed of: · C2-C8, especially C2-C4, mono- or unsaturated monocarboxylic acid, or 2-16, especially 2- An alkali salt of a dicarboxylic acid having 12 carbon atoms, preferably a titanium salt; preferably a calcium salt or an aluminum salt thereof, each of which is optionally hydrated 1 #, according to at least one of Claims 14-17; Composition, characterized in that the additive comprises one or more of the following group selected from the group consisting of: amprenylphenyl; - zinc diphosphosphates of organic chlorine compounds, sulfur, phosphorus or calcium borate, organic solvent feeds as high-pressure additives (Hochdmckedditive); C C | ~ǧ fsols, fatty acids, zinc acid esters or aryl or vegetable oils; - petroleum sulphonate dinonine titanium sulfonate or sorbitan esters as anti-corrosive agents; - benzotriazole or sodium salt as metal deactivators; polymethacyl polyisobutylene, lyo-dio-1-ene and polysaccharides as viscosity diluents; - molybdenum dipyl dithiocarbamate or rnollbene sulphide diacyldithylcarbamate or aromatic amines as anti-abrasive additives, - functional polymers such as oily amines, organic polyether and amide-based compounds or molybdenum dithiocarbarate as Friction Modifiers; and ·· polymer powders such as polyamides, polyimides or PfW, graphite, oxy-oxides, boron nitride, metal-sulphides such as molybdenum disulphide, witram disulfide or tungsten, mofibden, bismuth, orphan and zinc. inorganic salts of mixed sulfides, alkali and alkali solids such as calcium carbonate, sodium and calcium phosphates as solid lubricants. 19. A 14 · Ί8. Fitting according to at least one of Claims 1 to 8, characterized in that the lubricating grease is waterproof, that is: a) the end-of-line examination of the evaluation section 1-SO with the test DIN 51807-1 and b) the examination of the test in accordance with the evaluation DIM 1-8 of the evaluation phase 1-80. 2 #, from 14. Claims according to any one of the preceding claims. claims that the weight average molecular weight (V? w? weight) of the caloinomignin sulfonate is greater than 10: 080 g / mol, in particular greater than or equal to 12 µm, even greater than 15 808 g / mol, which independently contains 2 - $ 2 "% s, especially 4 - 10% w / w% (calculated as elemental sulfur) IsAr or also contains 5 to 15% by weight of calcium, particularly 8 to 15% by weight of calcium. Characterized by the fact that the lubricating grease contains a base oil based on high-yielding fnachwaohsende raw materials and / or which is made up of higher O-oxide-derived raw materials - 22. The composition according to at least one of claims 14 to 20, characterized in that the composition is a dripping puff. DIM determined according to ISO 2178 above 280. Use of the composition according to at least one of claims 14 to 22 for lubrication of at least one gear. Use of a composite according to at least one of the claims herein as a synchronous rotary shaft joint with lubricated hollow shaft shroud, pre-fabricated from thermoplastic polyester esters, as a material for lubrication of the cone.
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