EP3268455B1 - Verfahren zur herstellung von polyharnstoff-verdickten schmierfetten auf basis von lignin-derivaten, derartige schmierfette und deren verwendung - Google Patents

Verfahren zur herstellung von polyharnstoff-verdickten schmierfetten auf basis von lignin-derivaten, derartige schmierfette und deren verwendung Download PDF

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Publication number
EP3268455B1
EP3268455B1 EP16717236.0A EP16717236A EP3268455B1 EP 3268455 B1 EP3268455 B1 EP 3268455B1 EP 16717236 A EP16717236 A EP 16717236A EP 3268455 B1 EP3268455 B1 EP 3268455B1
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Prior art keywords
lignin
weight percent
base oil
lignin derivative
isocyanate
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EP16717236.0A
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German (de)
English (en)
French (fr)
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EP3268455A1 (de
Inventor
Thomas Litters
Florian Hahn
Torsten Goerz
Hans Jürgen ERKEL
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Fuchs SE
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Fuchs Petrolub SE
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Priority to PL16717236T priority Critical patent/PL3268455T3/pl
Publication of EP3268455A1 publication Critical patent/EP3268455A1/de
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    • 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
    • C10M169/00—Lubricating compositions characterised by containing as components a mixture of at least two types of ingredient selected from base-materials, thickeners or additives, covered by the preceding groups, each of these compounds being essential
    • C10M169/06—Mixtures of thickeners and additives
    • 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
    • C10M115/00—Lubricating compositions characterised by the thickener being a non-macromolecular organic compound other than a carboxylic acid or salt thereof
    • C10M115/08—Lubricating compositions characterised by the thickener being a non-macromolecular organic compound other than a carboxylic acid or salt thereof containing nitrogen
    • 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
    • C10M119/00—Lubricating compositions characterised by the thickener being a macromolecular compound
    • C10M119/24—Lubricating compositions characterised by the thickener being a macromolecular compound containing nitrogen
    • 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
    • C10M151/00—Lubricating compositions characterised by the additive being a macromolecular compound containing sulfur, selenium or tellurium
    • 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
    • C10M151/00—Lubricating compositions characterised by the additive being a macromolecular compound containing sulfur, selenium or tellurium
    • C10M151/04—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • 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
    • 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
    • C10M163/00—Lubricating compositions characterised by the additive being a mixture of a compound of unknown or incompletely defined constitution and a non-macromolecular compound, each of these compounds being essential
    • 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
    • C10M169/00—Lubricating compositions characterised by containing as components a mixture of at least two types of ingredient selected from base-materials, thickeners or additives, covered by the preceding groups, each of these compounds being essential
    • C10M169/02—Mixtures of base-materials and thickeners
    • 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
    • C10M2203/00—Organic non-macromolecular hydrocarbon compounds and hydrocarbon fractions as ingredients in lubricant compositions
    • C10M2203/10—Petroleum or coal fractions, e.g. tars, solvents, bitumen
    • C10M2203/1006—Petroleum or coal fractions, e.g. tars, solvents, bitumen used as base material
    • 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
    • C10M2203/00—Organic non-macromolecular hydrocarbon compounds and hydrocarbon fractions as ingredients in lubricant compositions
    • C10M2203/10—Petroleum or coal fractions, e.g. tars, solvents, bitumen
    • C10M2203/102—Aliphatic fractions
    • C10M2203/1025—Aliphatic fractions used as base material
    • 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
    • C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
    • C10M2209/12—Polysaccharides, e.g. cellulose, biopolymers
    • 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
    • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2215/10—Amides of carbonic or haloformic acids
    • C10M2215/102—Ureas; Semicarbazides; Allophanates
    • C10M2215/1023—Ureas; Semicarbazides; Allophanates used as base material
    • 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
    • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2215/10—Amides of carbonic or haloformic acids
    • C10M2215/102—Ureas; Semicarbazides; Allophanates
    • C10M2215/1026—Ureas; Semicarbazides; Allophanates used as thickening material
    • 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
    • C10M2217/00—Organic macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2217/04—Macromolecular compounds from nitrogen-containing monomers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M2217/045—Polyureas; Polyurethanes
    • C10M2217/0456—Polyureas; Polyurethanes used as thickening agents
    • 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
    • C10M2221/00—Organic macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
    • C10M2221/04—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M2221/041—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds involving sulfurisation of macromolecular compounds, e.g. polyolefins
    • 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
    • C10N2020/00—Specified physical or chemical properties or characteristics, i.e. function, of component of lubricating compositions
    • C10N2020/01—Physico-chemical properties
    • C10N2020/02—Viscosity; 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
    • C10N2030/02—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
    • C10N2030/08—Resistance to extreme temperature
    • 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
    • C10N2030/10—Inhibition of oxidation, e.g. anti-oxidants
    • 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
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/04—Oil-bath; Gear-boxes; Automatic transmissions; Traction drives
    • 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
    • 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
    • C10N2070/00—Specific manufacturing methods for lubricant compositions

Definitions

  • the invention relates to a process for the preparation of lubricating greases based on lignin derivatives thickened by a polyurea thickener, lubricating greases produced in this way and the use of such greases u.a. in gearboxes, constant velocity universal joint shafts and sealed rolling bearings.
  • the US 3249537 describes sodium lignosulfonate as a grease thickener in the presence of acetic acid, sodium hydroxide and / or lithium hydroxide, a longer chain fatty acid, a base oil and an amine additive.
  • the grease obtained with this composition is water-soluble or not sufficiently resistant to water for many applications.
  • the capsule material often makes the movements of the mutually moving parts or at least absorbs vibrations. This requires mobility and, in most cases, elasticity of the material, which must not be adversely affected by contact or interaction with the grease.
  • Calcium lignosulfonates as part of greases are also from the US 2011/0190177 A1 and the WO 2011/095155 A1 known.
  • the latter relates to a complex fat and the use in constant velocity universal joint shafts encapsulated by, inter alia, TPE bellows.
  • the former discloses the use of different thickening agents for calcium lignosulfonates, including polyureas.
  • the WO 2014046202 A1 describes a grease containing 1-20 wt% lignophenol derivatives, e.g. The structure: in the base oil. Polyurethane or polyurea thickeners are not mentioned.
  • the US 2013 / 0338049A1 discloses a grease composition containing lignin derivatives and various thickening agents, including polyurea thickeners in a mixture of base oils and additives.
  • the lignin derivatives are added to an already prepared polyurea grease.
  • lignin derivatives have considerable amounts of water, such as lignosulfonates 4 to 8 wt.%. This can lead to insufficient thermal stability of the lignin derivative-containing greases by evaporation of water and other volatile or easily decomposable components at higher application temperatures. In sealed or encapsulated grease points, this leads to an overpressure build-up, which can lead to damage of the seal or encapsulation or to a grease escape or to a water and dirt entry.
  • Tribochemically acting EP / AW additives used in today's polyurea and polyurethane fats account for a not inconsiderable share of the formulation costs and are thus often the price-driving factor for greases.
  • Many of these additives are prepared by elaborate multi-step synthesis procedures and their use is limited by their toxicological side effect, which occurs in many cases, both in the way they are used and in their use concentration in the final formulation. In some applications, for example in constant velocity universal joint shafts or in slow-moving and heavily loaded roller bearings, it is not possible to avoid insufficient lubrication conditions or contact of the friction partners with liquid lubricants by liquid additives.
  • solid lubricants based on inorganic compounds eg boron nitride, carbonates, phosphates or hydrogen phosphates
  • plastic powders eg PTFE
  • metal sulfides eg MoS 2
  • the greases should be thermally inert and the lignin derivatives should be distributed in these as a solid and homogeneous with small particle sizes.
  • the variant B2 is preferred.
  • the particular advantage of the variants B.1 and B.2 is that when working with an initial isocyanate excess, due to the multistage initially a complete Aminin reduction can be achieved and then at elevated temperature and in the presence of the lignin derivative time delay and the Abretician Excess isocyanate groups is possible.
  • the greases according to the invention have unexpectedly good properties when used as lubricating grease in plain and roller bearings, gearboxes, constant velocity joints and are well applied by means of lubrication systems and centralized lubrication systems to let.
  • the greases of the invention differ significantly from conventional fats.
  • the lubricating greases according to the invention are distinguished by a particular thermal stability, described by an evaporation loss according to DIN 58397-1 of ⁇ 8% after 48 hours at 150 ° C.
  • the greases of the invention are further characterized by a water content of less than 100 ppm, based on the amount of added lignin derivative, determined according to DIN 51777-1.
  • the lubricating greases according to the invention furthermore exhibit a particularly fine and homogeneous particle distribution, even if they were not treated with homogenizing processes customary in industrial production processes, such as tooth colloid mills and high-pressure homogenizers. If no step of heating the lignin derivative to over 120 ° C, on average, larger particles occur.
  • the size of the particles can be determined eg with a grindometer according to Hegman ISO 1524 .
  • the greases of the invention are characterized by an improved low temperature behavior, described by a flow pressure according to DIN 51805 at - 40 ° C, which is up to 25% lower than comparable lubricating greases, in which the lignosulfonate not miterhitzt in the presence of polyurea thickener or excess isocyanate has been.
  • the greases according to the invention are distinguished by improved conveyability and filtration properties. Both are important criteria for applications of greases in greasing systems or centralized lubrication systems.
  • the conveyability can be described by the shear viscosity (flow resistance) according to DIN 51810-1. It has been observed that this is about 10% lower at the same test temperature than comparable greases of comparable consistency in which the lignosulfonate in the presence of polyurea thickener or excess isocyanate was not heated to temperatures greater than 110 ° C.
  • the maximum particle size is usually smaller by more than 30% when tested by Grindometer according to Hegman ISO 1524.
  • the invention relates to a method in which according to the embodiment (B), or (B.1) and (B.2), lignin derivative and polyurea thickener or its starting materials, amine and isocyanate, together in the base oil temperatures of greater than 120 ° C for 30 min and longer, preferably greater than 170 ° C or even greater than 180 ° C, are exposed, in particular.
  • the polyurea thickener is prepared in the presence of the lignin derivative by reacting a mixture of isocyanates and amines (plus any alcohols) in the presence of the lignin derivative with each other and then by heating Temperatures greater than 120 ° C for 30 min and longer, more preferably greater than 170 ° C or even greater than 180 ° C, exposed, in particular for 30 min and longer.
  • the lignin derivative is added after the polyurea thickener from the isocyanate and the amine component (containing optionally also alcohols) is prepared completely or partially.
  • the amine component containing optionally also alcohols
  • the polyurea thickener is heated to a temperature of greater than 120 ° C for 30 min and longer, more preferably greater than 170 ° C or even greater than 180 ° C. especially for 30 minutes and longer.
  • the isocyanate excess is greater than 0.1%, preferably greater than 0.5%.
  • This is intended to bring about or promote a reaction with the lignin derivative by subsequent heating, in particular a reaction with the OH groups or other isocyanate-reactive functional groups of the lignin derivative.
  • the isocyanates are completely reacted with the amines, alcohols, reactive components of the lignin derivatives and optionally with any excess water.
  • post-crosslinking of the lubricating greases after production is prevented / reduced in use.
  • the heating process of the lignin derivative in the presence of the polyurea thickener surprisingly found that lignin derivative is then present in a more homogeneous distribution.
  • the isocyanate based on the molar amount of the amines or alcohols used for forming the polyurea fat, is added thereto in a molar excess, so that complete conversion of the amines and alcohols is ensured first, followed by residual isocyanate with reactive groups of the lignin -Derivats reacts. This is intended to achieve an additional thickening effect and a good aging stability of the greases.
  • diisocyanates are suitable for reacting with lignin derivatives
  • MDI was heated together with lignin sulfonate and thickened. This proves that the diisocyanates are able to crosslink lignin derivatives.
  • the reaction product of isocyanate and lignin derivative acts in addition to the polyurea thickener as an additional thickener for the grease.
  • the conversion to base grease takes place in a heated reactor, which can also be designed as an autoclave, in the base oil.
  • a heated reactor which can also be designed as an autoclave, in the base oil.
  • further constituents such as additives and / or additional base oil, are added to set the desired consistency or property profile.
  • the second step may be carried out in the reactor of the first step, but preferably the base grease from the reactor is transferred to one or more separate stirred tanks for cooling and mixing in the optionally further constituents.
  • the resulting grease is homogenized, and / or filtered and / or vented.
  • the lignin derivatives crosslink themselves by the heating process with the functional groups located in the lignin derivative and thereby escape volatile components such as hydroxyl-containing groups or CO 2, etc. This would explain the experimentally observed difference between evaporative loss and dehydration because the reduction in evaporation loss is greater than the amount of dehydration that would be expected, even if there is no excess of isocyanate.
  • Lignin is a complex polymer based on phenylpropane units, which are interlinked with each other with a range of different chemical bonds. Lignin occurs in plant cells together with cellulose and hemicellulose. Lignin itself is a cross-linked macromolecule. As monomer components of lignin, it is possible to identify essentially three types of monolignol monomers which differ from each other in their degree of methoxylation. These are p-cumaryl alcohol, coniferyl alcohol and sinapyl alcohol. These lignols are incorporated into the lignin structure in the form of hydroxyphenyl (H), guaiacyl (G), and syn-ring (S) units. Naked plants (gymnosperms) such as pine trees contain mostly G-units and small amounts of H-units.
  • H hydroxyphenyl
  • G guaiacyl
  • S syn-ring
  • lignins contain small amounts of incomplete or modified monolignols.
  • the primary function of lignins in plants is to provide mechanical stability by cross-linking the plant polysaccharides.
  • Lignin derivatives for the purposes of the present invention are degradation products or reaction products of lignin, which make the lignin isolated accessible or cleave and insofar typical products, such as those produced in papermaking.
  • lignin derivatives to be used according to the invention it is furthermore possible to distinguish between lignin obtainable from softwood or hardwood.
  • lignin derivatives obtainable from softwood are preferred. These have higher molecular weights and tend to result in drive shafts to greases with better life.
  • Sulfur-containing and sulfur-free processes are used to extract or digest lignins from lignocellulosic biomass.
  • Sulfur-containing processes are divided into the sulfite process and the sulfate process (Kraft process), in which the lignin derivatives are extracted from hardwoods or softwoods.
  • Lignosulfonate is a by-product of papermaking in the sulfite process .
  • comminuted wood chips are heated under pressure (5 to 7 bar) for wood chips for about 7 to 15 hours in the presence of calcium hydrogen sulfite solution and then the lignosulfonic acid in the form of calcium lignosulfonate is removed from the lignocellulose by a washing and precipitation process.
  • calcium hydrogen sulfite it is also possible to use magnesium, sodium or ammonium sulfite bases, which leads to the corresponding magnesium, sodium and ammonium salts of lignin sulfonic acid. Evaporation of the wash liquor yields the commercially available powdered lignosulfonates which can be used in the context of the present invention.
  • lignosulfonates are preferably calcium and / or sodium lignosulfonate or mixtures thereof are used.
  • Particularly suitable as lignin sulfonate are lignosulfonates having a molecular weight (M w, weight average) of preferably greater than 10,000, in particular greater than 12,000 or even greater than 15,000 g / mol, preferably used, for example greater than 10,000 to 65,000 / mol or 15,000-65,000 g / mol, which in particular 2 to 12% by weight, in particular 4 to 10% by weight, of sulfur (calculated as elemental sulfur) and / or 5 to 15% by weight, in particular 8 to 15% by weight of calcium (calculated Ca).
  • M w molecular weight
  • alkali or alkaline earth lignosulfonates or mixtures thereof may additionally be used.
  • Suitable calcium lignosulfonates are e.g. the commercially available products Norlig 11 D and Borrement Ca 120 from Borregard Ligno Tech or Starlig CP from von Ligno Star.
  • Suitable sodium lignosulfonates are Borrement NA 220 from Borregard Ligno Tech or Starlig N95P from Ligno Star.
  • sulfate or Kraftclar heated wood chips or shredded plant stems in pressure vessels for three to six hours at elevated pressure (7 to 10 bar) with essentially sodium hydroxide, sodium sulfide and sodium sulfate.
  • the lignin is cleaved by a nucleophilic attack of the sulfide anion and goes into so-called.
  • Black liquor soluble alkali lignin
  • suitable kraft lignins are Indulin AT from MWV Specialty Chemicals or Diwatex 30 FK, Diwatex 40 or Lignosol SD-60 from Borregard Ligno Tech (USA).
  • the power process is currently used in about 90% of world pulp production.
  • Kraft lignins are often further derivatized by sulfonation and amination.
  • a sub-variant of the force process is the Ligno Boost process .
  • the sulfate lignin is precipitated from a concentrated black liquor by lowering the pH or by stepwise introduction of carbon dioxide and addition of sulfuric acid ( P. Tomani & P Axegard, ILI 8th Formu Rome 2007 ).
  • the Organosolv process yields lignins and lignin derivatives from hardwoods and softwoods.
  • the commercially most commonly used Organosolv processes are based on digestion of the lignins with an alcohol-water mixture (ethanol-water) or with acetic acid mixed with other mineral acids. Also methods with phenol digestion and monoethanolamine digestion are known.
  • Organosolv lignins are often highly pure and insoluble in water, readily soluble in organic solvents and thus can be used even better as lignosulfonates or kraft lignins in lubricant formulations.
  • Suitable Organosolv lignins (CAS number 8068-03-9) are e.g. available from Sigma Aldrich.
  • soda lignins especially from annuals, such as agricultural residues such as bagasse or straw by digestion with sodium hydroxide solution. They are soluble in alkaline-aqueous media.
  • a lignin derivative suitable as a lubricant component is also Desilube AEP (pH 3.4 with sulfur-based acid groups) from Desilube Technology, Inc.
  • both soda and organosolv lignins have no sulfonate groups and lower ash content. They are thus even more suitable for chemical reaction with grease thickener components such as isocyanate.
  • a particular aspect of Organosolv lignins is that they have many phenolic OH groups with simultaneously low ash content and absence of sulfonate groups and thus are easier to implement with isocyanates than the other lignin derivatives.
  • alkali or alkaline earth metal hydroxides such as calcium hydroxide can be used to neutralize the acid groups of the lignin derivatives and thus provide an additional thickening effect and improved aging stability and elastomer compatibility.
  • the lignin derivative is acidic, Ca (OH) 2 , NaOH or amines may additionally be added to the lubricating grease.
  • Lignin derivatives are effective ingredients in greases and are now used to improve anti-wear and scuffing properties.
  • the lignin derivatives can be multifunctional components. Due to their high number of polar groups and aromatic structures, their polymeric structure and low solubility in all types of lubricating oils, powdered lignins and / or lignosulfonates are also suitable as solid lubricants in greases and lubricating pastes.
  • the phenolic hydroxyl groups contained in lignin and lignosulfonates provide an age-inhibiting effect.
  • the sulfur content in lignosulfonates promotes the EP / AW action in greases.
  • the weight average molecular weight is determined, for example, by size exclusion chromatography.
  • a suitable method is the SEC-MALLS method as described in the article of GE Fredheim, SM Braaten and BE Christensen, "Comparison of molecular weight and molecular weight distribution of softwood and hardwood lignosulfonates” published in "Journal of Wood Chemistry and Technology", Vol.23, No.2, pages 197-215, 2003 and the article "Molecular Weight Determination of Lignosulfonates by Size Exclusion Chromatography and Multi-angle Laser Scattering" by the same authors, published in Journal of Chromatography A, Volume 942, Issue 1-2, January 4, 2002, pages 191-199 (Mobile phase: phosphate-DMSO-SDS, stationary phase: Jordi-glucose DVB as described under 2.5).
  • the polyurea thickeners are composed of urea bonds and possibly polyurethane bonds. These are obtainable by reacting an amine component with an isocyanate component. The corresponding fats are then referred to as Polyharnstofffette.
  • the amine component comprises monoaminohydrocarbyl, di- or polyaminohydrocarbylene compounds, besides optionally other isocyanate-reactive groups, in particular monohydroxycarbyl, di- or polyhydroxyhydrocarbylene or aminohydroxyhydrocarbylene.
  • the hydrocarbyl or hydrocarbylene groups preferably each have 6 to 20 carbon atoms, more preferably 6 to 15 carbon atoms.
  • the hydrocarbylene group preferably has aliphatic groups. Suitable representatives are for example in the EP 0508115 A1 called.
  • the isocyanate component comprises mono- or polyisocyanates, wherein the polyisocyanates are preferably hydrocarbons having two or more isocyanate groups.
  • the isocyanates have 5 to 20, preferably 6 to 15 carbons and preferably contain aromatic groups.
  • Either the amine component is difunctional or polyfunctional or the isocyanate component or both.
  • the polyurea thickeners are the reaction product of diisocyanates with C6 to C20 hydrocarbyl (mono) amines or a mixture with hydrocarbyl (mono) alcohols.
  • the reaction products are with respect to the ureas e.g. obtainable from the reaction of C6 to C20 hydrocarbylamines and a disocyanate.
  • the latter are also referred to as polyurea-polyurethane fats, which are included in the term polyurea fats in the context of the present invention.
  • reaction products of mono-isocyanates plus, if appropriate, including diisocyanates, with diamines and optionally additionally alcohols are also possible.
  • the polyurea thickeners are typically not polymeric in character but are e.g. Dimers, trimers or tetramers.
  • diureas based on 4,4'-diphenylmethane diisocyanate (MDI) or m-tolylene diisocyanate (TDI) and aliphatic, aromatic and cyclic amines or tetraureas based on MDI or TDI and aliphatic, aromatic and cyclic mono- and diamines.
  • MDI 4,4'-diphenylmethane diisocyanate
  • TDI m-tolylene diisocyanate
  • R-NCO monoisocyanate
  • the monoisocyanates are preferably added along with the lignin derivative during grease manufacture when thickening according to the polyurea or polyurea-polyurethane components is completed to react with functional groups of the lignin derivative to additionally thickening components.
  • addition of R-NCO and lignin and / or lignin sulfonate is also possible prior to the addition of the polyurea or polyurea polyurethane components.
  • bentonites such as montmorillonite (whose sodium ions are optionally exchanged or partially exchanged by organically modified ammonium ions), aluminosilicates, clays, hydrophobic and hydrophilic silicic acid, oil-soluble polymers (eg polyolefins, poly (meth) acrylates, polyisobutylenes, Polybutenes or polystyrene copolymers) can be used as co-thickener.
  • the bentonites, aluminosilicates, clays, silicic acid and / or oil-soluble polymers may be added to make the base fat or added later as an additive in the second step.
  • Simple, mixed or complex soaps based on Li, Na, Mg, Ca, Al, Ti salts.
  • Carboxylic acids or sulfonic acids may be added during base grease manufacture or later as an additive. Alternatively, these soaps can be formed in situ during the production of the fats.
  • compositions according to the invention optionally further contain additives as additives.
  • additives for the purposes of the invention are antioxidants, anti-wear agents, corrosion inhibitors, detergents, dyes, lubricity improvers, adhesion promoters, viscosity additives, friction reducers, high-pressure additives and metal deactivators.
  • lignin derivatives it is beneficial for the distribution and effect of lignin derivatives, if they are chemically or mechanically integrated during or immediately after the reaction phase as an additional structural element in situ in the thickener structure.
  • the grease compositions of this invention contain conventional anti-corrosive, oxidative, and anti-metallope additives which act as chelates, radical scavengers, UV transducers, reaction layer formers, and the like. Also additives which improve the hydrolysis resistance of ester base oils, e.g. Carbodiimides or epoxides can be added.
  • solid lubricants may, for example, polymer powder such as polyamides, polyimides or PTFE, melamine cyanurate, graphite, metal oxides, boron nitride, silicates, eg magnesium silicate hydrate (talc), sodium tetraborate, potassium tetraborate, metal sulfides such.
  • polymer powder such as polyamides, polyimides or PTFE, melamine cyanurate, graphite, metal oxides, boron nitride, silicates, eg magnesium silicate hydrate (talc), sodium tetraborate, potassium tetraborate, metal sulfides such.
  • molybdenum disulfide tungsten disulfide or mixed sulfides based on tungsten, molybdenum, bismuth, tin and zinc
  • inorganic salts of alkali and alkaline earth metals such as calcium carbonate, sodium and calcium phosphates
  • the desired advantageous lubrication properties can be adjusted by the use of lignin derivatives, without having to use solid lubricants. In many cases, these can be dispensed with completely or at least can be significantly minimized. As far as solid lubricants are used, graphite is advantageously used.
  • Suitable base oils are customary lubricating oils which are liquid at room temperature.
  • the base oil preferably has a kinematic viscosity of 20 to 2500 mm 2 / s, in particular 40 to 500 mm 2 / s at 40 ° C.
  • the base oils can be classified as mineral oils or synthetic oils.
  • mineral oils are considered to be naphthenic and paraffinic mineral oils as defined by API Group I.
  • synthetic oils include polyethers, esters, polyesters, polyalphaolefins, polyethers, perfluoropolyalkylethers (PFPAE), alkylated naphthalenes, and alkylaromatics and mixtures thereof.
  • the polyether compound may have free hydroxyl groups, but may also be fully etherified or end groups esterified and / or prepared from a starting compound having one or more hydroxy and / or carboxyl groups (-COOH).
  • polyphenyl ethers optionally alkylated, as sole components or even better as mixed components.
  • esters of an aromatic di-, tri- or tetracarboxylic acid with one or more C2 to C22 alcohols present in the mixture, esters of adipic acid, sebacic acid, trimethylolpropane, neopentyl glycol, pentaerythritol or dipentaerythritol with aliphatic branched or unbranched, saturated or unsaturated C2 to C22 carboxylic acids, C18 dimer acid esters with C2 to C22 alcohols, complex esters, as individual components or in any desired mixture.
  • the base grease for the preparation of the base grease to temperatures of about 110 ° C, in particular heated above 120 ° C or better greater than 170 ° C.
  • the conversion to the base fat takes place in a heated reactor, which can also be designed as an autoclave or vacuum reactor.
  • a second step by cooling the formation of the thickener structure is completed and, if appropriate, further constituents, such as additives and / or base oil, are added to set the desired consistency or the desired property profile.
  • the second step may be carried out in the reactor of the first step, but preferably the base grease from the reactor is transferred to a separate stirred tank for cooling and mixing in the optional further constituents.
  • the resulting grease is homogenized, filtered and / or vented.
  • a high process temperature of greater than 120 ° C, in particular greater than 170 ° C is additionally ensured that the still registered in the lignosulfonate residual moisture is completely evaporated from the reaction medium.
  • the greases of the invention are particularly suitable for use in or for constant velocity universal joint, plain bearings, bearings and gearbox. It is a particular aspect of the present invention to arrive at cost optimized grease formulations for highly loaded lubrication points such as, in particular, constant velocity joints which have good compatibility with bellows constructed of e.g. thermoplastic polyetherester (TPE) and chloroprene (CR), while high efficiency, low wear and long life.
  • TPE thermoplastic polyetherester
  • CR chloroprene
  • the bellows material including capsule materials which are in contact with the lubricant, according to a further embodiment of the invention is a polyester, preferably a thermoplastic copolyester elastomer comprising hard segments with crystalline properties and a melting point above 100 ° C and soft segments having a glass transition temperature of less than 20 ° C, preferably less than 0 ° C, have.
  • a polyester preferably a thermoplastic copolyester elastomer comprising hard segments with crystalline properties and a melting point above 100 ° C and soft segments having a glass transition temperature of less than 20 ° C, preferably less than 0 ° C, have.
  • TPE polychloroprene rubber and thermoplastic polyesters
  • TEEE topographical ether-ester-elastomer
  • the latter are commercially available under the trade names Arnitel® from DSM, Hytrel® from DuPont and PIBI-Flex® from P-Group.
  • WO 85/05421 A1 describes such a suitable polyetherester material for bellows, based on polyether esters. Also, a bellows body as an injection molded part of a thermoplastic polyester elastomer is in the DE 35 08 718 A called.
  • the hard segments are derived, for example, from at least one aliphatic diol or polyol and at least one aromatic di- or polycarboxylic acid, the soft segments having elastic properties, for example from ether polymers such as polyalkylene oxide glycols or non-aromatic dicarboxylic acids and aliphatic diols. Such compounds are referred to, for example, as Copolyetherester.
  • Copolyetherester compositions are used in components, for example, when the component made therefrom is subjected to frequent deformation or vibration.
  • Very well known applications in this context are bellows or bellows for the protection of drive shafts and transmission shafts, joint columns and suspension units as well as sealing rings. In such applications, the material also frequently or continuously comes into contact with lubricants such as greases.
  • the bellows is produced by injection blow molding, injection extrusion or extrusion blow molding, with annular rubber parts possibly being placed in the mold at the two future clamping points.
  • the resistance of the copolyetherester composition to the effects of oils and fats is one of the reasons for their wide use in addition to their ease of processing into relatively complex geometries.
  • Another particular aspect of the invention is the use of lubricating greases in rolling bearings, including those with high load bearing and high operating temperatures.
  • the requirements for these greases are described inter alia in DIN 51825 and in ISO 12924.
  • a method for testing the wear protection effect of lubricating greases in roller bearings is described by DIN 51819-2.
  • Methods for testing the service life of greases at a selected application temperature are described, for example, in accordance with DIN 51806, DIN 51821-2, ASTM D3527, ASTM D3336, ASTM D4290, and IP 168, and by the ROF test method of SKF.
  • lubricating greases have a good service life at 150 ° C if they pass the test according to DIN 51821-2 at 150 ° C with a 50% test bearing failure probability of greater than 100 hours at 150 ° C.
  • the batch was heated to 180 ° C with stirring and the volatiles evaporated. The temperature of 180 ° C was maintained for 30 minutes. It was tested by IR spectroscopy for complete conversion of the isocyanate by observation of the NCO band between 2250 and 2300 cm -1 . It was then cooled. In the cooling phase, the batch was mixed with additives at 80 ° C. After adjusting the batch to the desired consistency by adding the remaining amount of base oil provided, the final product was homogenized.
  • the lignin derivative (7.0 wt% calcium lignin sulfonate) was transferred to the reactor and stirred.
  • the batch was heated to 180 ° C with stirring and the volatiles were evaporated. The temperature of 180 ° C was maintained for 30 min.
  • IR spectroscopic reaction control during the heating and holding time can be demonstrated that the isocyanate excess is gradually reacted and completely disappeared after the end of the hold time at 180 ° C.
  • the amine / base oil mixture from the separate stirred tank was added to the reactor and the mixture was heated with stirring to 110 ° C in the IR spectrum at 110 ° C, the isocyanate band between 2250 and 2300 cm -1 completely disappeared.
  • the batch was heated to 180 ° C with stirring. The temperature of 180 ° C was maintained for 30 minutes.
  • Example A2 is somewhat softer compared to Example A1 (penetration value higher), but shows a worse wear and load bearing capacity (SRV increase run, Table 5). Also, the oil separation is higher.
  • reaction time was heated to 140 ° C and 7.1 wt.% Calciumligninsulfonat added, heated to 180 ° C and held for 30 min at this temperature and the volatiles evaporated and by IR spectroscopy for complete conversion of the isocyanate by observation the NCO band between 2250 and 2300 cm -1 tested.
  • the batch was cooled and additives were added at 80 ° C. After adjusting the batch to the desired consistency by adding the remaining base oil, the final product was homogenized.
  • the temperature of 180 ° C was maintained for 30 min and was checked by IR spectroscopy for complete conversion of the isocyanate by observation of the NCO band between 2250 and 2300 cm -1 . It was then cooled.
  • 5.53 wt.% Calcium lignosulfonate were heated to 120 ° C in 1/6 of the intended base oil quantity with stirring and the water contained evaporated for 2 h.
  • the Calciumligninsulfonat / base oil mixture from the separate container was added in the cooling phase at 80 ° C in the reactor produced in the di-urea at 80 ° C. Subsequently, additives were added. After adjusting the batch to the desired consistency by adding the remaining base oil, the final product was homogenized.
  • a 250 ml graduated cylinder with a fine graduation is filled with 100 ml of the grease to be tested and placed in a drying oven for 3 h at 150 ° C. Stored residual water (evaporating substances) causes the fat to rise. The percentage rise of the grease in the graduated cylinder is noted after 3 hours in 5% increments.

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EP16717236.0A 2015-03-09 2016-03-09 Verfahren zur herstellung von polyharnstoff-verdickten schmierfetten auf basis von lignin-derivaten, derartige schmierfette und deren verwendung Active EP3268455B1 (de)

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