US20160002557A1 - Process for preparing a urea grease - Google Patents

Process for preparing a urea grease Download PDF

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Publication number
US20160002557A1
US20160002557A1 US14/765,946 US201414765946A US2016002557A1 US 20160002557 A1 US20160002557 A1 US 20160002557A1 US 201414765946 A US201414765946 A US 201414765946A US 2016002557 A1 US2016002557 A1 US 2016002557A1
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Prior art keywords
formula
compound
grease
urea
carbon atoms
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US14/765,946
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English (en)
Inventor
Stefan Daegling
Alexander HELLAWELL
Eurydice KONE
Alexander MASSEY
Howard Brian Mead
Don VAN ZWIETEN
Ton Visser
Robert James Wilkinson
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Shell USA Inc
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Shell Oil Co
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Assigned to SHELL OIL COMPANY reassignment SHELL OIL COMPANY ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: MEAD, HOWARD BRIAN, HELLAWELL, Alexander, MASSEY, ALEXANDER, WILKINSON, ROBERT JAMES, DAEGLING, STEFAN, KONE, Eurydice, VAN ZWIETEN, Don, VISSER, TON
Publication of US20160002557A1 publication Critical patent/US20160002557A1/en
Abandoned legal-status Critical Current

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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
    • C10M105/00—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound
    • C10M105/56—Lubricating compositions characterised by the base-material being a non-macromolecular organic 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
    • 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
    • C10M177/00—Special methods of preparation of lubricating compositions; Chemical modification by after-treatment of components or of the whole of a lubricating composition, not covered by other classes
    • 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
    • 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
    • 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 preparing a urea grease.
  • Urea greases are used in a variety of applications including bearings for constant-velocity joints, ball joints, wheel bearings, alternators, cooling fans, ball screws, linear guides of machine tools, sliding areas of construction equipment, and bearings and gears in steel equipment and various other industrial mechanical facilities.
  • Urea greases typically have excellent heat and oxidation resistance, and can extend the lifetime of bearings.
  • Urea greases contain low molecular weight organic compounds, sometimes referred to as polyureas, that are typically synthesized from isocyanates and amines.
  • a diisocyanate and a monoamine can be used to form a diurea:
  • a diisocyanate and a diamine can be used to form a tetraurea:
  • a diisocyanate, an alcohol and a diamine can be used to form a triurea-urethane:
  • Urea greases are formed by carrying out these reactions in a base oil, thereby directly providing the grease product wherein the urea thickener is dispersed throughout the base oil.
  • the reaction of the diisocyanate and the amine does not require any heat and proceeds at a good rate at room temperature. There are no reaction byproducts that must be removed.
  • the diisocyanate reagents are highly toxic and volatile and require special treatment and handling equipment. It is desirable to find an alternative route for the manufacture of urea greases that avoids the use of diisocyanate reagents.
  • the invention provides a process for preparing a urea grease comprising one or more steps in which a compound of formula (I), a compound of formula (II) and a compound of formula (III) are reacted:
  • R 4 and R 2 are chosen from hydrocarbyl having from 1 to 30 carbon atoms, or R 4 and R 2 are linked and form a hydrocarbylene group having from 1 to 30 carbon atoms, R 3 is chosen from hydrocarbyl comprising from 2 to 30 carbon atoms and R 4 is hydrocarbylene comprising from 2 to 30 carbon atoms;
  • urea grease may be prepared by reacting compounds (I), (II) and (III) wherein at least one of the reaction steps takes place in the presence of a base oil.
  • FIG. 1 is a reaction scheme showing the preparation of a urea grease according to the invention.
  • FIG. 2 is a reaction scheme showing the preparation of a urea grease according to the invention.
  • FIG. 3 is a reaction scheme showing the preparation of a urea grease according to the invention.
  • FIG. 4 is a reaction scheme showing the preparation of a urea grease according to the invention.
  • hydrocarbyl refers to a monovalent organic radical comprising hydrogen and carbon and may be aliphatic, aromatic or alicyclic, for example, but not limited to, aralkyl, alkyl, aryl, cycloalkyl, alkylcycloalkyl, or a combination thereof, and may be saturated or olefinically unsaturated (one or more double-bonded carbons, conjugated or non-conjugated).
  • hydrocarbylene refers to a divalent organic radical comprising hydrogen and carbon and may be aliphatic, aromatic or alicyclic, for example, but not limited to, aralkyl, alkyl, aryl, cycloalkyl or alkylcycloalkyl, and may be saturated or olefinically unsaturated (one or more double-bonded carbons, conjugated or non-conjugated).
  • the invention provides a process for the preparation of a urea grease.
  • a compound of formula (I), a compound of formula (II) and a compound of formula (III) are reacted:
  • R 1 and R 2 are chosen from hydrocarbyl having from 1 to 30 carbon atoms, or R 1 and R 2 are linked and form a hydrocarbylene group having from 1 to 30 carbon atoms.
  • R 1 and R 2 are preferably hydrocarbyl groups or a hydrocarbylene group comprising only hydrogen and carbon atoms, but it is possible that R 1 and R 2 may also comprise heteroatom substituents such as halo, nitro, hydroxyl or alkoxy substituents, particularly if one or more of R 1 or R 2 is an aryl group.
  • R 1 and R 2 are chosen from aryl having from 6 to 12 carbon atoms and alkyl having from 1 to 12 carbon atoms, or R 1 and R 2 are linked and form an alkylene group having from 1 to 12 carbon atoms.
  • R 1 and R 2 are chosen from phenyl and substituted-phenyl groups having from 6 to 12 carbon atoms and alkyl groups having from 1 to 12 carbon atoms, or R 1 and R 2 are linked and form an alkylene group having from 1 to 6 carbon atoms.
  • Substituted phenyl includes methyl-substituted or ethyl-substituted phenyl (preferably in the para or ortho positions) or ethoxy-substituted phenyl.
  • R 1 and R 2 are both phenyl or R 1 and R 2 are linked and form an ethylene group, i.e. the compound of formula (I) is diphenylene carbonate or ethylene carbonate.
  • R 1 and R 2 are suitably chosen such that R 1 ⁇ OH and R 2 —OH (or HO—R 1 —R 2 —OH) are compounds that may be readily removed from the reaction mixture.
  • R 3 is chosen from hydrocarbyl comprising from 2 to 30 carbon atoms.
  • R 3 preferably comprises only hydrogen and carbon atoms, but it is possible that R 3 may also comprise heteroatom substituents such as halo, nitro, hydroxyl or alkoxy substituents, particularly if R 3 is an aryl group.
  • R 3 is aryl having from 6 to 12 carbon atoms or is alkyl comprising from 2 to 18 carbon atoms.
  • the compound of formula (II) is chosen from octylamine, dodecylamine(laurylamine), tetradecylamine(myristylamine), hexadecylamine, octadecylamine(tallow amine, also referred to as stearylamine), oleylamine, aniline, benzyl amine, p-toluidine, p-chloro-aniline or m-xylidine.
  • R 4 is hydrocarbylene comprising from 2 to 30 carbon atoms.
  • R 4 preferably comprises only hydrogen and carbon atoms, but it is possible that R 4 may also comprise heteroatom substituents such as halo, nitro, hydroxyl or alkoxy substituents particularly if R 4 is an arylene group.
  • R 4 is arylene comprising from 6 to 12 carbon atoms or alkylene comprising from 2 to 12 carbon atoms.
  • the compound of formula (III) is chosen from arylene comprising from 6 to 12 carbon atoms. Preferred compounds of formula (III) are shown below:
  • a compound of formula (I), a compound of formula (II) and a compound of formula (III) are reacted in one step in the presence of a base oil.
  • the reaction takes place in two steps and the second step takes place in the presence of a base oil.
  • the process for preparing a urea grease comprises steps of:
  • step (b1) is carried out in the presence of a base oil.
  • the process for preparing a urea grease comprises steps of:
  • step (b2) is carried out in the presence of a base oil.
  • step (a1) the compound of formula (I) reacts with the compound of formula (II):
  • step (a1) If R 1 and R 2 are linked and form a hydrocarbylene group, then there will be just one product. If R 1 and R 2 are hydrocarbyl groups (and are not linked), then an alcohol byproduct will result in step (a1) and this byproduct is preferably removed before step (b1).
  • a diurea grease is suitably prepared by reacting compounds of formula (I) and (II) in step (a1) and subsequently reacting the product of step (a1) with a compound of formula (III) in step (b1):
  • step (a1) the compounds of formula (I) and (II) are additionally reacted with a compound of formula (IV):
  • step (a1) wherein R 5 is hydrocarbylene comprising from 2 to 30 carbon atoms.
  • step (b1) The product of step (a1) is then reacted with a compound of formula (III) in step (b1):
  • R 5 preferably comprises only hydrogen and carbon atoms, but it is possible that R 5 may also comprise heteroatom substituents such as halo, nitro, hydroxyl or alkoxy substituents.
  • R 5 is preferably arylene comprising from 6 to 12 carbon atoms or alkylene comprising from 2 to 12 carbon atoms.
  • Preferred compounds of formula (IV) include ethylenediamine, propylenediamine, butylenediamine, pentylenediamine and hexamethylenediamine.
  • step (a1) the compounds of formula (I) and (II) are additionally reacted with a compound of formula (V) and a compound of formula (VI):
  • R 6 and R 7 are independently chosen from hydrocarbyl comprising from 2 to 30 carbon atoms.
  • step (a1) The product of step (a1) is then reacted with a compound of formula (III) in step (b1):
  • R 6 preferably comprises only hydrogen and carbon atoms, but it is possible that R 6 may also comprise heteroatom substituents such as halo, nitro, hydroxyl or alkoxy substituents.
  • R 6 is preferably alkylene or alkenylene comprising from 2 to 24 carbon atoms.
  • Preferred compounds of formula (V) include 1-dodecanol(lauryl alcohol), 1-tetradecanol(myristyl alcohol), 1-hexadecanol(cetyl(or palmityl)alcohol), 1-octadecanol(stearyl alcohol), cis-9-octadecen-1-ol(oleyl alcohol), 9-octadecadien-1-ol(unsaturated palmitoleyl alcohol), 12-octadecadien-1-ol(linoleyl alcohol).
  • R 7 preferably comprises only hydrogen and carbon atoms, but it is possible that R 7 may also comprise heteroatom substituents such as halo, nitro, hydroxyl or alkoxy substituents.
  • R 7 preferably arylene comprising from 6 to 12 carbon atoms or alkylene comprising from 2 to 12 carbon atoms.
  • Preferred compounds of formula (VI) include ethylenediamine, propylenediamine, butylenediamine, pentylenediamine and hexamethylenediamine.
  • step (b1) Before the product of step (a1) is used in step (b1) it is preferable to remove any unreacted compounds of formula (I) and (II), any solvent that may have been used and any byproducts (especially R 1 —OH and R 2 —OH compounds). Removal is suitably achieved using vacuum.
  • step (a2) the compound of formula (I) reacts with the compound of formula (III):
  • step (a2) If R 1 and R 2 are linked and form a hydrocarbylene group, then there will be just one product. If R 1 and R 2 are hydrocarbyl groups (and are not linked), then an alcohol byproduct will result in step (a2) and this byproduct is preferably removed before step (b2).
  • a diurea grease is suitably prepared by reacting compounds of formula (I) and (III) in step (a2) and subsequently reacting the product of step (a2) with a compound of formula (II) in step (b2) in the presence of a base oil:
  • step (a2) the compounds of formula (I) and (III) are additionally reacted with a compound of formula (IV):
  • step (a2) the compound of formula (I) will react with the compound of formula (III), and the compound of formula (I) will react with the compound of formula (IV).
  • step (b2) the reaction products of step (a2) are then reacted with a compound of formula (II):
  • step (a2) the compounds of formula (I) and (III) are additionally reacted with compounds of formula (V) and (VI):
  • step (a2) the compound of formula (I) will react with the compound of formula (III), the compound of formula (I) will react with the compound of formula (V) and the compound of formula (I) will react with the compound of formula (VI).
  • step (b2) the reaction products of step (a2) are then reacted with a compound of formula (II):
  • step (b2) Before the product(s) of step (a2) is/are used in step (b2) it is preferable to remove any unreacted compounds of formula (I) and (III), any solvent that may have been used and any byproducts (especially R 1 —OH and R 2 —OH compounds). Removal is suitably achieved using vacuum or adequate solvent washes.
  • step (a1) and (a2) The preferred reaction conditions in step (a1) and (a2) will be affected by the choice of the compound (I). If compound (I) is diphenyl carbonate, then step (a1) or (a2) preferably takes place without solvent or in the presence of a solvent such as toluene or dimethylformamide. The reaction preferably takes place in the presence of a catalyst such as diphenylphosphinic acid. Phenol will be produced as a byproduct of the reaction. The phenol byproduct should be removed, e.g. by use of a vacuum.
  • compound (I) is dimethyl carbonate
  • a catalyst such as dibutyl tin methoxide, dibutyl tin dilaurate or tin (II) octoate.
  • Other catalysts that could be used include potassium t-butoxide, copper (II) acetylacetonate, DABCO BL11 and DABCO LV33.
  • step (b1) and (b2) will be affected by the choice of the compound (I). If compound (I) is diphenyl carbonate then the reactants are preferably heated to at least 90° C. and more preferably about 100° C. The reaction is preferably carried out in the absence of catalyst. If compound (I) is dimethyl carbonate then the reactants are preferably heated to at least 130° C. and more preferably about 140° C. The reaction is preferably carried out in the presence of a catalyst such as dibutyl tin dilaurate. The inventors have found that additional heating is often necessary to transform the reaction product of step (b1) or (b2) into a grease. Preferably the reaction products of step (b1) or (b2) are heated to at least 170° C. and then cooled.
  • a catalyst such as dibutyl tin dilaurate
  • the base oil that is present in at least one of the reaction steps may be of mineral origin, synthetic origin, or a combination thereof.
  • Base oils of mineral origin may be mineral oils, for example, those produced by solvent refining or hydroprocessing.
  • Base oils of synthetic origin may typically comprise mixtures of C 10 -C 50 hydrocarbon polymers, for example, polymers of alpha-olefins, ester type synthetic oils, ether type synthetic oils, and combinations thereof.
  • Base oils may also include Fischer-Tropsch derived highly paraffinic products.
  • mineral base oils include paraffinic base oils and naphthenic base oils.
  • Paraffinic base oils typically have a proportion of carbons in aromatic structure (Ca) in a range of from 1 to 10%, in naphthenic structure (Cn) in a range of from 20 to 30% and in paraffinic structure (Cp) in a range of from 60 to 70%.
  • Naphthenic base oils typically have a proportion of carbons in aromatic structure (Ca) in a range of from 1 to 20%, in naphthenic structure (Cn) in a range of from 30 to 50% and in paraffinic structure (Cp) in a range of from 40 to 60%.
  • Suitable examples of base oils include medium viscosity mineral oils, high viscosity mineral oils, and combinations thereof.
  • Medium viscosity mineral oils have a viscosity generally in a range of from 5 mm 2 /s centistokes (cSt) at 100° C. to 15 mm 2 /s (cSt) at 100° C., preferably in a range of from 6 mm 2 /s (cSt) at 100° C. to 12 mm 2 /s (cSt) at 100° C., and more preferably in a range of from 7 mm 2 /s (cSt) at 100° C. to 12 mm 2 /s (cSt) at 100° C.
  • High viscosity mineral oils have a viscosity generally in a range of from 15 mm 2 /s (cSt) at 100° C. to 40 mm 2 /s (cSt) at 100° C. and preferably in a range of from 15 mm 2 /s (cSt) at 100° C. to 30 mm 2 /s (cSt) at 100° C.
  • mineral oils that may conveniently be used include those sold by member companies of the Shell Group under the designations “HVI”, “MVIN”, or “HMVIP”.
  • Polyalphaolefins and base oils of the type prepared by the hydroisomerisation of wax for example, those sold by member companies of the Shell Group under the designation “XHVI” (trade mark), may also be used.
  • the urea grease that is the product of the process of the invention comprises a urea thickener and a base oil.
  • the urea grease comprises a weight percent of urea based on the total weight of urea grease in a range of from 2 weight percent to 25 weight percent, more preferably in a range of from 3 weight percent to 20 weight percent, and most preferably in a range of from 5 weight percent to 20 weight percent.
  • the product of the process of the invention is a urea grease.
  • the base grease that results from step (b1) or step (b2) is subjected to further finishing procedures such as homogenisation, filtration and de-aeration.
  • a urea grease prepared according to a process of the invention may comprise one or more additives, in amounts normally used in this field of application, to impart certain desirable characteristics to the urea grease including, for example, oxidation stability, tackiness, extreme pressure properties, corrosion inhibition, reduced friction and wear, and combinations thereof.
  • the additives are preferably added to the base grease before the finishing procedures. Most preferably, the base grease is homogenised, then the additives are added, and then the grease is subjected to further homogenization.
  • Suitable additives include one or more extreme pressure/antiwear agents, for example zinc salts such as zinc dialkyl or diaryl dithiophosphates, borates, substituted thiadiazoles, polymeric nitrogen/phosphorus compounds made, for example, by reacting a dialkoxy amine with a substituted organic phosphate, amine phosphates, sulphurised sperm oils of natural or synthetic origin, sulphurised lard, sulphurised esters, sulphurised fatty acid esters, and similar sulphurised materials, organo-phosphates for example according to the formula (OR) 3 P ⁇ O where R is an alkyl, aryl or aralkyl group, and triphenyl phosphorothionate; one or more overbased metal-containing detergents, such as calcium or magnesium alkyl salicylates or alkylarylsulphonates; one or more ashless dispersant additives, such as reaction products of polyisobutenyl succinic anhydride and
  • a urea grease prepared according to a process of the invention may comprise from 0.1 weight percent to 15 weight percent, preferably from 0.1 weight percent to 5 weight percent, more preferably from 0.1 weight percent to 2 weight percent, and even more preferably from 0.2 weight percent to 1 weight percent of one or more additives based on the total weight of urea grease.
  • urea greases produced by the process of the invention are suitably used in typical applications for urea greases such as in constant-velocity joints, ball joints, wheel bearings, alternators, cooling fans, ball screws, linear guides of machine tools, sliding areas of construction equipment, and bearings and gears in steel equipment and various other industrial mechanical facilities.
  • a urea grease may be prepared by a process comprising one or more steps in which a compound of formula (I), a compound of formula (II) and a compound of formula (III) are reacted:
  • R 4 and R 2 are chosen from hydrocarbyl having from 1 to 30 carbon atoms, or R 1 and R 2 are linked and form a hydrocarbylene group having from 1 to 30 carbon atoms, R 3 is chosen from hydrocarbyl comprising from 2 to 30 carbon atoms and R 4 is hydrocarbylene comprising from 2 to 30 carbon atoms;
  • FIGS. 1 , 2 , 3 and 4 Reaction schemes showing proposed four proposed syntheses of urea greases are shown in FIGS. 1 , 2 , 3 and 4 .
  • FIG. 1 shows a process wherein diphenyl-carbonate (2) is reacted with ethylenediamine (4) and octylamine (1) without solvent under nitrogen atmosphere. After the reaction is completed the excess phenol is removed in vacuum. The two intermediates (3,5) are than combined to the final tetraurea (7) by introducing the methylene diphenyl diamine (6) under the same conditions and in the presence of a base oil. The reaction product is heated to 170° C. to form a tetraurea grease.
  • FIG. 2 shows a process wherein octylamine (1) and ethylenediamine (4) are added to a ice-cooled solution of ethylenecarbonate (8) in water.
  • the reaction is catalysed with (Bu 2 Sn(OMe) 2 ).
  • the solvent and excess amines are removed under vacuum and the products 9 and 10 are isolated.
  • the products 9 and 10 and the methylene diphenyl diamine (6) are connected at 150° C. catalysed by (Bu 2 Sn(OMe) 2 ) and the presence of a base oil.
  • the resulting ethylene glycol is removed in vacuum.
  • the reaction product is heated to 170° C. to form a tetraurea grease.
  • FIG. 3 shows a process wherein dimethylcarbonate (1) and 4,4′-methylenedianiline (2) are reacted at 80° C. in the presence of potassium t-butoxide. Methanol will be removed as a byproduct.
  • the diphenylcarbamate product (3) is reacted with octylamine (4) in the presence of a base oil and dibutyltin dilaureate at 100° C. to provide a grease product which is a diurea in base oil.
  • the reaction product is heated to 170° C. to form a diurea grease.
  • FIG. 4 shows a process wherein diphenylcarbonate (1) and 4,4′-methylenedianiline (2) are reacted at 100° C. in the presence of diphenylphosphinic acid. Phenol will be removed as a byproduct.
  • the diphenylcarbamate product (3) is reacted with octylamine (4) in the presence of a base oil at 100° C. to provide a grease product which is a diurea in base oil.
  • the reaction product is heated to 170° C. to form a diurea grease.
  • the product was worked up by adding dimethyl ether, filtering and washing with dimethyl ether. A yield of 91-94% diphenylcarbamate was achieved.
  • 4,4′-methylenedianiline was heated with potassium t-butoxide (4.4 eq) in dimethyl carbonate (neat) at 80° C. for 0.5 h to give dimethylcarbamate (89%) after filtration and washing with water.
  • Dimethylcarbamate (65 g) prepared according to example 3a was reacted with octylamine and dibutyltin dilaureate (added over several days) in base oil at 140° C. for 7 days to give the diurea product together with some mono-urea. 498 g of a grease was isolated. The properties of the grease were measured and are shown in Table 1.
  • Example 1c 260 264 4 295 Example 1d 215 253 38 >300 (sample 1)
  • Example 1d 207 249 42 >300 (sample 2)
  • Example 2 219 247 28 >300 (sample 1)
  • Example 2 227 254 27 >300 (sample 2)
  • Example 3b 238 336 98 235 (sample 1)
  • Example 3b 215 333 118 232 (sample 2)
  • the delta penetration is as low as possible, and low values were achieved by some of the greases.
  • the worked penetration values range from 247 to 340 which will give greases that would typically fall into the category of NLGI grade 1, 2 or 3.
  • the dropping point is desirably as high as possible and several of the greases gave dropping points in excess of 300.

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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)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
US14/765,946 2013-02-08 2014-02-07 Process for preparing a urea grease Abandoned US20160002557A1 (en)

Applications Claiming Priority (3)

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EP13154677.2 2013-02-08
EP13154677 2013-02-08
PCT/EP2014/052454 WO2014122273A1 (fr) 2013-02-08 2014-02-07 Procédé de préparation d'une graisse à base d'urée

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US (1) US20160002557A1 (fr)
EP (1) EP2954035B1 (fr)
JP (1) JP6211100B2 (fr)
CN (1) CN104981536A (fr)
BR (1) BR112015017754A2 (fr)
RU (1) RU2646606C2 (fr)
WO (1) WO2014122273A1 (fr)

Cited By (1)

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Publication number Priority date Publication date Assignee Title
CN113677782A (zh) * 2019-04-26 2021-11-19 引能仕株式会社 润滑油组合物

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WO2018092806A1 (fr) * 2016-11-16 2018-05-24 出光興産株式会社 Composition de graisse pour équipement doté d'un dispositif d'alimentation en graisse automatique, et procédé de production associé
JP7382250B2 (ja) 2020-02-14 2023-11-16 株式会社ネオス ポリウレアポリウレア化合物とこれを含む組成物ならびにポリウレア硬化物、およびポリウレア硬化物を含む成形フィルムならびに成形品
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JP6211100B2 (ja) 2017-10-11
WO2014122273A1 (fr) 2014-08-14
BR112015017754A2 (pt) 2017-07-11
EP2954035A1 (fr) 2015-12-16
EP2954035B1 (fr) 2016-12-21
CN104981536A (zh) 2015-10-14

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