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 PDFInfo
- 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
- Authority
- HU
- Hungary
- Prior art keywords
- weight
- calcium
- acid
- salt
- base
- Prior art date
Links
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
Landscapes
- 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)
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE102010006745A DE102010006745A1 (en) | 2010-02-02 | 2010-02-02 | Greases containing lignosulfonate, their preparation and use |
Publications (1)
Publication Number | Publication Date |
---|---|
HUE026690T2 true HUE026690T2 (en) | 2016-07-28 |
Family
ID=43983746
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
HUE11711018A HUE026690T2 (en) | 2010-02-02 | 2011-01-31 | Lubricating greases containing lignosulfonate, the production thereof, and the use thereof |
Country Status (20)
Country | Link |
---|---|
US (1) | US20120302472A1 (en) |
EP (1) | EP2531587B9 (en) |
JP (1) | JP5856078B2 (en) |
KR (1) | KR101833854B1 (en) |
CN (1) | CN102770513B (en) |
AU (1) | AU2011212763B2 (en) |
BR (1) | BR112012019181B1 (en) |
CA (1) | CA2788157C (en) |
DE (1) | DE102010006745A1 (en) |
DK (1) | DK2531587T3 (en) |
ES (1) | ES2561821T3 (en) |
HR (1) | HRP20160072T1 (en) |
HU (1) | HUE026690T2 (en) |
MX (1) | MX2012008960A (en) |
PL (1) | PL2531587T3 (en) |
PT (1) | PT2531587E (en) |
RS (1) | RS54610B1 (en) |
RU (1) | RU2554873C2 (en) |
SI (1) | SI2531587T1 (en) |
WO (1) | WO2011095155A1 (en) |
Families Citing this family (43)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS6265910A (en) * | 1985-09-13 | 1987-03-25 | Nippon Cement Co Ltd | Production of composite powder of silicon nitride and silicon carbide |
US8507421B2 (en) | 2010-02-02 | 2013-08-13 | Fuchs Lubricants Co. | Lubricating greases and process for their production |
CN102433189A (en) * | 2011-10-24 | 2012-05-02 | 中国石油化工股份有限公司 | Composite calcium-sulfonate-based lubricating grease composition and preparation method thereof |
US9222050B1 (en) * | 2012-02-29 | 2015-12-29 | Rand Innovations, Llc | Lubricant composition, method of preparing the same, and firearm cleaner including the same |
JP5659390B2 (en) * | 2012-09-21 | 2015-01-28 | 住鉱潤滑剤株式会社 | Lubricant composition |
JP5704574B2 (en) * | 2012-09-24 | 2015-04-22 | 住鉱潤滑剤株式会社 | Lubricant composition |
US9228151B1 (en) * | 2012-11-07 | 2016-01-05 | Rand Innovations, Llc | Lubricant additive composition, lubricant, and method of preparing the same |
JP5889823B2 (en) * | 2013-03-28 | 2016-03-22 | 住鉱潤滑剤株式会社 | Grease composition for constant velocity joint and constant velocity joint |
JP5916654B2 (en) * | 2013-03-28 | 2016-05-11 | 住鉱潤滑剤株式会社 | Grease composition for constant velocity joint and constant velocity joint |
JP6051097B2 (en) * | 2013-04-26 | 2016-12-27 | 出光興産株式会社 | Grease manufacturing method |
EP3009496A1 (en) * | 2013-06-12 | 2016-04-20 | NSK Ltd. | Grease composition and rolling bearing |
CN105408647B (en) * | 2013-07-19 | 2018-12-04 | Ntn株式会社 | rolling bearing |
MX2016002519A (en) * | 2013-09-02 | 2016-06-16 | Nippon Steel & Sumitomo Metal Corp | Composition for forming lubricating coating film, and threaded joint for steel pipe. |
JP6223863B2 (en) * | 2014-02-27 | 2017-11-01 | 昭和シェル石油株式会社 | Grease composition |
JP6274435B2 (en) * | 2014-09-22 | 2018-02-07 | 住鉱潤滑剤株式会社 | Lubricant composition |
US10752859B2 (en) * | 2015-02-06 | 2020-08-25 | Shell Oil Company | Grease composition |
BR112017017308B1 (en) * | 2015-02-11 | 2022-06-28 | Shell Internationale Research Maatschappij B.V. | GREASE COMPOSITION AND USE OF A GREASE COMPOSITION |
DE102015103440A1 (en) | 2015-03-09 | 2016-09-15 | Fuchs Petrolub Se | Process for the preparation of polyurea-thickened lubricating greases based on lignin derivatives, greases of this kind and their use |
EP3165589A1 (en) | 2015-11-04 | 2017-05-10 | Henkel AG & Co. KGaA | Powder lubricant based on zinc salts of fatty acids and use thereof |
CN108350385B (en) | 2015-11-04 | 2021-08-10 | 汉高股份有限及两合公司 | Powder lubricant based on fatty acids and fatty acid glycerides and use thereof |
CN105441165A (en) * | 2015-11-27 | 2016-03-30 | 蚌埠海明压铸机有限公司 | Durable lubricating oil for engine |
CN105419912A (en) * | 2015-11-27 | 2016-03-23 | 蚌埠海明压铸机有限公司 | Anti-wear lubricating oil |
CN105441167A (en) * | 2015-11-27 | 2016-03-30 | 蚌埠海明压铸机有限公司 | Anti-oxidation and anti-corrosive lubricating oil |
CN105441166A (en) * | 2015-11-27 | 2016-03-30 | 蚌埠海明压铸机有限公司 | Lubricating oil for engine |
CN105441170A (en) * | 2015-11-30 | 2016-03-30 | 蚌埠市华科机电有限责任公司 | Rust-proof lubricating oil |
CN105441169A (en) * | 2015-11-30 | 2016-03-30 | 蚌埠市华科机电有限责任公司 | Lubricating oil for anti-wear engine |
JP2016084483A (en) * | 2016-02-16 | 2016-05-19 | 住鉱潤滑剤株式会社 | Grease composition and constant velocity joint |
JP2016130318A (en) * | 2016-03-16 | 2016-07-21 | 住鉱潤滑剤株式会社 | Grease composition, as well as constant velocity joint |
CN107236581A (en) * | 2017-07-06 | 2017-10-10 | 广西柳工机械股份有限公司 | High-performance graphene complex grease |
US10626343B1 (en) * | 2017-11-17 | 2020-04-21 | Brave Response Shooting, LLC | Animal-based hydrocarbon firearm lubricant |
CN108531248A (en) * | 2018-06-05 | 2018-09-14 | 朱东洋 | A kind of wear-resisting anti-hardening preparation of greases method |
DE102018008362A1 (en) * | 2018-07-09 | 2020-01-09 | Klüber Lubrication München Se & Co. Kg | Environmentally friendly grease for steel cables |
RU2688928C1 (en) * | 2018-10-01 | 2019-05-23 | Федеральное государственное бюджетное образовательное учреждение высшего образования Иркутский государственный университет путей сообщения (ФГБОУ ВО ИрГУПС) | Method of producing anti-tearing additive for heavily loaded friction assemblies |
CN109825345B (en) * | 2019-02-19 | 2021-12-24 | 上海金兆节能科技有限公司 | High-temperature-resistant lubricant and preparation method thereof |
RU2698457C1 (en) * | 2019-06-21 | 2019-08-27 | Публичное акционерное общество "НК "Роснефть" - МЗ "Нефтепродукт" | Multipurpose complex grease |
DE102020117671B4 (en) | 2020-07-03 | 2022-06-09 | Fuchs Petrolub Se | Lubrication points comprising a polyurea grease composition and a seal comprising a fluorinated elastomer sealing material and the use of the polyurea grease composition for a lubrication point comprising such a seal |
DE102020008047A1 (en) | 2020-07-03 | 2022-01-05 | Fuchs Petrolub Se | Polyurea lubricating greases containing carbonates and their use |
CN112410101A (en) * | 2020-11-30 | 2021-02-26 | 新乡市恒星科技有限责任公司 | Precise high-molecular special lubricating grease and preparation method thereof |
CN113122354B (en) * | 2021-04-20 | 2023-08-15 | 中国石油化工股份有限公司 | Composite calcium-based lubricating grease and preparation method thereof |
CN113355148B (en) * | 2021-05-28 | 2022-12-20 | 中国石油化工股份有限公司 | Lubricant for automobile driving shaft hub bearing joint surface and preparation method thereof |
CN113403127A (en) * | 2021-06-08 | 2021-09-17 | 郑州市欧普士科技有限公司 | Environment-friendly anti-corrosion grease for overhead conductor and preparation method thereof |
DE102021133469B3 (en) | 2021-12-16 | 2022-08-25 | Fuchs Petrolub Se | Process for preparing lithium complex soap and lithium calcium complex soap greases |
CN114540106A (en) * | 2022-03-02 | 2022-05-27 | 北京市政建设集团有限责任公司 | Sealing grease for main bearing of shield tunneling machine and preparation method thereof |
Family Cites Families (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2976242A (en) * | 1955-04-01 | 1961-03-21 | Exxon Research Engineering Co | Lubricating grease compositions |
US3249537A (en) * | 1963-05-16 | 1966-05-03 | Exxon Research Engineering Co | Lignosulfonate lubricants |
US4409112A (en) * | 1981-12-23 | 1983-10-11 | Dresser Industries, Inc. | Lubricant, slow speed, high load |
CA2027241A1 (en) * | 1989-10-24 | 1991-04-25 | Andrew B. Law | Stabilized metal salt/3-isothiazolone combinations |
JPH11131086A (en) * | 1997-10-28 | 1999-05-18 | Nippon Koyu:Kk | Lubricating grease composition |
RU2224011C1 (en) * | 2002-12-02 | 2004-02-20 | Федеральное государственное унитарное предприятие "Московское машиностроительное производственное предприятие "Салют" | Hot or half-hot metal forming grease |
CN100404655C (en) * | 2003-11-13 | 2008-07-23 | 中国石油化工股份有限公司 | Composite lithium base lubricant and its preparing method |
CN100549147C (en) * | 2006-07-31 | 2009-10-14 | 中国石油化工股份有限公司 | Grease composition |
JP5101374B2 (en) * | 2008-04-02 | 2012-12-19 | 中央油化株式会社 | Calcium complex grease |
-
2010
- 2010-02-02 DE DE102010006745A patent/DE102010006745A1/en not_active Ceased
-
2011
- 2011-01-31 WO PCT/DE2011/000087 patent/WO2011095155A1/en active Application Filing
- 2011-01-31 PL PL11711018T patent/PL2531587T3/en unknown
- 2011-01-31 PT PT117110189T patent/PT2531587E/en unknown
- 2011-01-31 SI SI201130721T patent/SI2531587T1/en unknown
- 2011-01-31 BR BR112012019181A patent/BR112012019181B1/en active IP Right Grant
- 2011-01-31 CA CA2788157A patent/CA2788157C/en active Active
- 2011-01-31 ES ES11711018.9T patent/ES2561821T3/en active Active
- 2011-01-31 EP EP11711018.9A patent/EP2531587B9/en active Active
- 2011-01-31 KR KR1020127023089A patent/KR101833854B1/en active IP Right Grant
- 2011-01-31 CN CN201180008171.3A patent/CN102770513B/en active Active
- 2011-01-31 RS RS20160037A patent/RS54610B1/en unknown
- 2011-01-31 RU RU2012136909/04A patent/RU2554873C2/en active
- 2011-01-31 DK DK11711018.9T patent/DK2531587T3/en active
- 2011-01-31 JP JP2012550318A patent/JP5856078B2/en active Active
- 2011-01-31 MX MX2012008960A patent/MX2012008960A/en active IP Right Grant
- 2011-01-31 HU HUE11711018A patent/HUE026690T2/en unknown
- 2011-01-31 US US13/576,857 patent/US20120302472A1/en not_active Abandoned
- 2011-01-31 AU AU2011212763A patent/AU2011212763B2/en not_active Ceased
-
2016
- 2016-01-22 HR HRP20160072TT patent/HRP20160072T1/en unknown
Also Published As
Publication number | Publication date |
---|---|
BR112012019181A2 (en) | 2018-03-27 |
US20120302472A1 (en) | 2012-11-29 |
CN102770513B (en) | 2015-09-30 |
RU2012136909A (en) | 2014-03-10 |
WO2011095155A1 (en) | 2011-08-11 |
KR101833854B1 (en) | 2018-03-05 |
ES2561821T3 (en) | 2016-03-01 |
JP5856078B2 (en) | 2016-02-09 |
AU2011212763B2 (en) | 2013-10-17 |
PT2531587E (en) | 2016-02-26 |
EP2531587B9 (en) | 2016-10-05 |
CN102770513A (en) | 2012-11-07 |
RS54610B1 (en) | 2016-08-31 |
KR20120139730A (en) | 2012-12-27 |
AU2011212763A1 (en) | 2012-09-06 |
MX2012008960A (en) | 2012-10-15 |
CA2788157A1 (en) | 2011-08-11 |
RU2554873C2 (en) | 2015-06-27 |
DE102010006745A1 (en) | 2011-08-04 |
CA2788157C (en) | 2018-06-26 |
PL2531587T3 (en) | 2016-06-30 |
EP2531587A1 (en) | 2012-12-12 |
EP2531587B1 (en) | 2015-11-04 |
DK2531587T3 (en) | 2016-01-25 |
JP2013518929A (en) | 2013-05-23 |
HRP20160072T1 (en) | 2016-04-08 |
BR112012019181B1 (en) | 2018-09-11 |
SI2531587T1 (en) | 2016-04-29 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
HUE026690T2 (en) | Lubricating greases containing lignosulfonate, the production thereof, and the use thereof | |
JP5943479B2 (en) | Grease composition | |
US10618865B2 (en) | Organometallic salt composition, a method for its preparation and a lubricant additive composition | |
JP7095124B2 (en) | Environmentally friendly steel rope grease | |
CN105623797A (en) | Weak-smell low-corrosion gear lubricant additive composition and preparation method thereof | |
US11473032B2 (en) | Constant velocity joint having a boot | |
US11932821B2 (en) | Use of organometallic salt compositions for alleviating the formation of white etching cracks | |
US11591537B2 (en) | Lubricating grease comprising metal soaps and metal complex soaps based on R-10-hydroxyoctadecanoic acid | |
US20170145340A1 (en) | Constant Velocity Joint Having A Boot | |
US20200224115A1 (en) | Molybdenum-containing composition | |
CN112424320B (en) | Lubricant composition | |
CN1854269A (en) | Biological-degradable lubricating grease |