Classifications

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

Definitions

• the invention relates to a process for producing lubricating greases that contain calcium lignin sulfonate, lubricating 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 chemical bonds. Lignin is present in plant cells together with cellulose and hemicellulose. Lignin itself is a cross-linked macromolecule with average molecular weights of for example at least 10,000 g/mol (weight average).
• monolignol monomers that can be identified as monomer components of lignin, and they differ in the degree of their methoxylation. They are p-coumaryl alcohol, coniferyl alcohol and sinapyl alcohol. These lignols are incorporated in the lignin structure in the form of hydroxyphenyl (H)-, guaiacyl (G)- and syringal (S) units. Naked-seeded plants (gymnosperms) such as pine trees contain mostly G units and low proportions of H units. All lignins contain small amounts of incomplete or modified monolignols.
• Lignin sulfonate is obtained as a by-product of paper manufacturing using the sulfite process.
• wood that has been reduced to wood chips is heated for about 7 to 15 hours in the presence of calcium hydrogen sulfite liquor and under pressure (for example 5 to 7 bar) and then the ligninsulfonic acid is removed from the lignocellulose in the form of calcium lignin sulfonate in a washing and precipitation process.
• Liquors of magnesium, sodium or ammonium sulfide can also be used instead of calcium hydrogen sulfite, and these produce the corresponding magnesium, sodium and ammonium salts of ligninsulfonic acid.
• 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 animal feed industry and as dispersing or complexing agents in other fields.
• 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 lubricating greases both as cost-effective structure forming agents and as additives to promote wear resistance, reduce friction and protect against ageing, and at the same time to lend the lubricating greases good water resistance.
• lignin sulfonate means that the use of other common lubricant additives and solid lubricants, particularly MoS 2 , may be minimised or entirely dispensed with.
• first a precursor stage (base grease) is prepared by mixing at least
• Components with low boiling point are those components that boil at temperatures up to about 100° C. under normal pressure, such as water or C1- to C4-alcohols.
• the mixture is preferably heated to temperatures above 120° C., or preferably above 180° C.
• the conversion to base grease takes place in a heated reactor, which may also be constructed as an autoclave or vacuum reactor.
• a second step the formation of the thickener structure is completed by cooling and any additional components such as additives and/or base oil 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 transferred from the reactor to a separate stirred tank reactor for cooling and for mixing in the additional components, if any.
• the lubricating grease obtained in this way may be homogenised, filtered and/or deaerated.
• Preferred substances are Ca/Li—, Li/Ca— and calcium-thickened 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 the lubricating grease structure via a thermal process in such manner that it is present in highly homogeneous, oil-insoluble form and results in high dropping point temperatures.
• 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 be prevented in order to obtain a lubricating grease containing lignin sulfonate with good water resistance and at the same time a high dropping temperature. For this reason, the use of sodium lignin 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: 1979-04). Water resistance is further understood to mean that the grease conforms to rating level 1-80 (test at 80° C.) in the test in accordance with DIN 51807-2 (version 1990-03).
• Standard lubricating oils that are liquid at room temperature are suitable for use as base oils.
• the base oil preferably has a kinematic viscosity from 20 to 2500 mm 2 /s, particularly from 40 to 500 mm 2 /s at 40° C.
• the base oils may be classified as mineral oils or synthetic oils.
• Mineral 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, classified as API Group II and III are also suitable.
• polyethers examples include polyethers, esters, polyalphaolefins, polyglycols and alkyl aromatics and mixtures thereof.
• the polyether compound may contain free hydroxyl groups, but it may also be wholly etherised or terminal group esterified and/or it may be produced from a starter compound having one or more hydroxy and/or carboxyl groups (—COOH).
• Polyphenyl ethers, whether alkylated or not, are also possible as the sole component, or better still as components of a mixture.
• Esters of an aromatic di-, tri- or tetracarboxylic acid with one or more C2- to C22 alcohols present in mixture alcohols, esters of adipic acid, sebacic acid, trimethylolpropane, neopentyl glycol, pentaerythritol or dipentaerythritol with aliphatic, branched or linear, saturated or unsaturated C2 to C22 carboxylic acids, C18 dimer acid esters with C2 to C22 alcohols, complex esters, as single components or in any mixture thereof, are also suitable for use.
• the soaps 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 monocarboxylic 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 acid or behenic acid and preferably 12-hydroxystearic acid.
• 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 acid group to achieve better dispersion.
• the soap is converted into a complex soap by the presence of a complexing agent.
• the complex soaps according to the invention presence of a complexing agent
• have higher dropping points for example higher than 200° C. (DIN ISO 2176).
• Appropriate quantities for the addition of the complexing agent are from 0.5 to 20 wt %, particularly 0.5 to 10 wt %.
• Complexing agent (a) is preferably solely a calcium salt, particularly if this is used as calcium acetate to produce the base grease.
• Acetic acid and propionic acid are particularly suitable for use as monocarboxylic acids.
• Hydroxybenzoic acids such as parahydroxybenzoic acid, salicylic acids, 2-hydroxy-4-hexylbenzoic acid, metahydroxybenzoic acid, 2,5-dihydroxybenzoic acid (gentisic acid), 2,6-dihydroxybenzoic acid (gamma-resorcylic acid) or 4-hydroxy-4-methoxybenzoic acid are also suitable.
• dicarboxylic acids are adipic acid (C 6 H 10 O 4 ), sebacic acid (C 10 H 18 O 4 ), azelaic acid (C 9 H 16 O 4 ) and/or 3-tert.-butyl-adipic acid (C 10 H 18 O 4 ).
• borate (b) Possible substances for use as the borate (b) would include for example metaborate, 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.
• bentonites such as montmorillonite (in which some or all of the sodium ions may have been substituted with ammonium ions), aluminosilicates, clays, silicic acid (e.g. aerosil), oil-soluble polymers (e.g., polyolefins, poly(meth)acrylates, polyisobutylenes, polybutenes or PS) or also di- and polyureas may also be used as co-thickeners.
• the bentonites, aluminosilicates, clays, silicic acid and/or oil-soluble polymers may be added to produce the base grease or introduced as additives later, in the second step.
• the di- and polyureas may be introduced as additives.
• the compounds according to the invention may also contain other additives as additional substances.
• additional substances for the purposes of the invention are antioxidants, anti-wear agents, corrosion protection agents, detergents, dyes, lubrication enhancers, viscosity additives, friction reducers and high-pressure additives.
• the lubricating grease compounds according to the invention also contain usual additives for protection against corrosion, oxidation and attack by metals, which function as chelating compounds, radical scavengers, UV converters, reaction layer forming agents and the like.
• Solid lubricants may be selected for example from the group of polymer powders such as polyamides, polyimides or PTFE, graphite, metal oxides, boron nitride, metal sulfides such as molybdenum sulfide, tungsten disulfide or sulfide mixtures with tungsten, molybdenum, bismuth, tin and zinc base, inorganic salts of alkali and alkaline earth metals, such as calcium carbonate, sodium and calcium phosphates.
• polymer powders such as polyamides, polyimides or PTFE, graphite, metal oxides, boron nitride, metal sulfides such as molybdenum sulfide, tungsten disulfide or sulfide mixtures with tungsten, molybdenum, bismuth, tin and zinc base, inorganic salts of alkali and alkaline earth metals, such as calcium carbonate, sodium
• Solid lubricants may be divided into the following four groups: compounds with a lattice layer structure, such as molybdenum disulfide and tungsten disulfide, graphite, hexagonal boron nitride and certain metal halides; oxidic and hydroxidic 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 lubricants may be omitted entirely, or at least significantly reduced. If solid lubricants are used, graphite is the most favourable.
• Lignin 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 15,000-65,000 g/mol and particularly containing 2 to 12 wt %, particularly 4 to 10 wt %, sulfur (calculated as elemental sulfur) and/or 5 to 15 wt %, particularly 8 to 15 wt % calcium (calculated Ca).
• Mw molecular weight
• the average molecular weight (weight average) is determined for example by size exclusion chromatography.
• a suitable method is the SEC-MALLS method as described in the article by G. E, Fredheim, S. M. Braaten and B. E. Christensen, “Comparison of molecular weight and molecular weight distribution of softwood and hardwood lignosulfonates” published in “Journal of Wood Chemistry and Technology”, Vol.
• Suitable calcium sulfonates are for example the commercially available products Norlig 11 D and Borrement Ca 120 produced by Borregard Lignotech.
• 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.
• lignin sulfonate was observed to have surprisingly synergistic effects with other solid lubricants, for example with graphite or calcium carbonate.
• lignin sulfonates serve as multifunctional components for lubricants. Due to the large number of polar groups and aromatic structures they contain, their polymer structure and their low solubility in all types of lubricating oils, lignin sulfonates are suitable for use not only as a thickener component but also as solid lubricants in lubricating greases and lubricating pastes. Their sulfur content also enhances their EP/AW effect in the lubricating greases and the phenolic structures provide an age-inhibiting effect.
• the lignin sulfonate structure is predominantly planar.
• 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 particularly suitable for use in or for constant velocity joint shafts, rolling bearings and gearboxes.
• the lubricating greases are also suitable for total loss lubrication in the environmentally sensitive area (for example in mining or agriculture).
• the first lubricating grease has been formulated using calcium lignin sulfonate that differs from the prior art in that it assures long operating life and good levels of efficiency entirely without the use of MoS 2 and other organic and inorganic molybdenum compounds.
• a special aspect of the present invention is that it may be used to obtain cost-optimised lubricating 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.
• TPE thermoplastic polyether esters
• CR chloroprenes
• 460 g tallow fatty acid, 445 g beef tallow, 460 g calcium acetate, 27.7 g trisodium phosphate, 27.7 g calcium borate and 168 g calcium hydroxide and 920 g calcium lignin sulfonate (Norlig 11 D powder manufactured by Borregard Lignotech) were placed in a reactor in 14,000 g of a base oil mixture and 150 ml 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 during 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 constant velocity joint shaft grease, for example.
• the grease obtained thereby is suitable for use as rolling bearing grease, for example.
• This base was heated to 225° 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 cooling phase. After the base was adjusted to the desired consistency by adding 3125 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 rolling bearing grease, for example.
• example formulations I and J are similar to the production of example H but with the use of different quantities of calcium-12 hydroxy stearate, calcium acetate and calcium lignin sulfonate and different compositions of ester base oils.
• the lubricating greases obtained thereby are made on the basis of predominantly renewable raw materials.

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• Chemical & Material Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• General Chemical & Material Sciences (AREA)
• Oil, Petroleum & Natural Gas (AREA)
• Organic Chemistry (AREA)
• Lubricants (AREA)
• Sliding-Contact Bearings (AREA)
• General Details Of Gearings (AREA)
• Rolling Contact Bearings (AREA)

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