US3346496A - Lubricants containing carbodiimides as antioxidants - Google Patents

Lubricants containing carbodiimides as antioxidants Download PDF

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US3346496A
US3346496A US455606A US45560665A US3346496A US 3346496 A US3346496 A US 3346496A US 455606 A US455606 A US 455606A US 45560665 A US45560665 A US 45560665A US 3346496 A US3346496 A US 3346496A
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carbodiimide
oil
diphenyl
carbodiimides
isopropyl
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Neumann Wolfram
Lohmar Walther
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Bayer AG
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Bayer AG
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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
    • C10M1/00—Liquid compositions essentially based on mineral lubricating oils or fatty oils; Their use as lubricants
    • C10M1/08—Liquid compositions essentially based on mineral lubricating oils or fatty oils; Their use as lubricants with 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
    • C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
    • C10M2209/10—Macromolecular compoundss obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M2209/103—Polyethers, i.e. containing di- or higher polyoxyalkylene groups
    • 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
    • C10M2209/10—Macromolecular compoundss obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M2209/103—Polyethers, i.e. containing di- or higher polyoxyalkylene groups
    • C10M2209/104—Polyethers, i.e. containing di- or higher polyoxyalkylene groups of alkylene oxides containing two carbon atoms only
    • 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
    • C10M2209/10—Macromolecular compoundss obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M2209/103—Polyethers, i.e. containing di- or higher polyoxyalkylene groups
    • C10M2209/107—Polyethers, i.e. containing di- or higher polyoxyalkylene groups of two or more specified different alkylene oxides covered by groups C10M2209/104 - C10M2209/106
    • 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
    • C10M2209/10—Macromolecular compoundss obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M2209/103—Polyethers, i.e. containing di- or higher polyoxyalkylene groups
    • C10M2209/109—Polyethers, i.e. containing di- or higher polyoxyalkylene groups esterified
    • 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
    • C10M2215/02—Amines, e.g. polyalkylene polyamines; Quaternary amines
    • C10M2215/06—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to carbon atoms of six-membered aromatic rings
    • C10M2215/064—Di- and triaryl amines
    • 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
    • C10M2215/086—Imides
    • 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
    • C10M2215/14—Containing carbon-to-nitrogen double bounds, e.g. guanidines, hydrazones, semicarbazones
    • 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
    • C10M2215/22—Heterocyclic nitrogen compounds
    • 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
    • C10M2215/22—Heterocyclic nitrogen compounds
    • C10M2215/221—Six-membered rings containing nitrogen and carbon only
    • 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
    • C10M2215/22—Heterocyclic nitrogen compounds
    • C10M2215/225—Heterocyclic nitrogen compounds the rings containing both nitrogen and oxygen
    • 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
    • C10M2215/22—Heterocyclic nitrogen compounds
    • C10M2215/225—Heterocyclic nitrogen compounds the rings containing both nitrogen and oxygen
    • C10M2215/226—Morpholines
    • 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
    • C10M2215/28—Amides; Imides
    • 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
    • C10M2215/30—Heterocyclic compounds
    • 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

Definitions

  • the present invention relates to lubricant additives; more particularly it concerns lubricant additives which consist essentially of carbodiimides.
  • the carbodiimides to be used as lubricant additives may be monoor poly-carbodiimides and may belong to the aliphatic, cycloaliphatic or aromatic series.
  • monocarbodiimides are the following: di-isopropyl-carbodiimide, di-n-butyl-carbodiimide, methyl-tert.-butyl-carbodiimide, dicyclohexyl carbodiimide, diphenyl-carbodiimide, di-p-tolyl-carbodiimide and 4,4'-didodecyl-diphenyl-carbodiimide.
  • diphenyl-monocarbodiimides which carry in the phenyl radicals in orthoposition to the carbodiimide group substituents, e.g. alkyl, alkoxy, aryl and aralkyl radicals, such as 2,2'-diethyl-diphenyl carbodiimide, 2,2'-di-is0propyl-diphenylcarbodiimide, 2,2'-diethoxy-diphenyl-carbodiimide, 2,'6,2,6-tetraethyl 'cliphenyl-carbodiimide, 2,6,2',6'-tetraisopropyl-diphenyl-carbodiimide, 2,6,2,6'-tetraethyl-3,3-dichloro-diphenyl-carbodiimide, 2,2-diethyl-6,6'-dichloro-diphenylcarbodiimide, 2,6,2,6'-tetra-isobut
  • Suitable polycarbodiimides are, for example, tetramethylene-w,w'-bis(tert.-butyl-carbodiimide), hexamethylene-w,w'-bis-(tert.-butyl-carbodiimide), tetrarnethylene-w,w'-bis-(phenyl-carbodiimide) and those compounds which may be obtained by heating aromatic polyisocyanates such as 1,3-di-isOpropyl-phenylene-2,4di-is cyanate, 1-methyl-3,5-diethyl-phenylene-2,4-diisocyanate and 3,5,3,5-tetra-isopropyl-diphenylmethane-4,4-di-isocyanate, in the presence of tertiary amines, basically reacting metal compounds, carboxylic acid metal salts or nonbasic organometal compounds at a temperature of at least 120 C., according to the process of German Patent No. 1,156,
  • carbodiimides With the aid of carbodiimides it is possible to improve substantially lubricants of a great variety of types, in particular their resistance to oxidative attacks. This applies in the first instance to lubricants which are produced from mineral oils, but also to lubricating oils of synthetic origin which are polyethers or polyether esters, but especially to lubricating oils based on synthetic polyethers or polyether esters which contain -(CH O groups alternating several times with one another or with other alkyleneO groups and which are described in German Patent No. 1,071,872.
  • the carbodiimides are, at the same time, also efiective as protective agents against corrosion and are, moreover, capable of keeping the decomposition products formed during the lubricating process in solution.
  • the amounts of carbodiimides required in each case can be easily determined in preliminary experiments; in general, additives of 1 to 2 percent by weight, referred to the lubricant, have proved to be sufiicient.
  • the lubricant additives to be used according to the present invention are compatible with other lubricant additives, e.g. with detergents, agents for increasing the resistance of the lubricating film, and also agents for improving the solidification point and the viscosity.
  • An especially advantageous embodiment of the present invention consists in that the carbodiimides can be added to the lubricants in combination with diphenylamines known as antioxidants, such as 4,4'-di-(methylbenzyl)-diphenylamine, and/ or hydroxyquinolines such as S-hydroxyquinoline.
  • Example 1 100 parts of a naphthene-basic mineral oil are mixed with 1 part of 2,6,2,6'-tetra-is0propyl-diphenyl-carbodiimide.
  • the resistance of the mineral oil to oxidative attacks is thus substantially improved; the action of the carbodiimide used is further increased by the addition of 0.2 part 4,4'-('dimethyl-benzyl)-diphenylamine and/or 8-hydroxyquinoline.
  • Table I where the neutralisation numbers (mg. KOH/g. oil) of the oils mixed with the various additives are listed after oxidative action.
  • a oil without additive B oil with 1% 2,6,2,6 '-tetra-isopropyl-diphenyl-carbodiimide C oil with 0.2% 4,4'-dimethylbenzyldiphenylamine D oil with 1% 2,6,2,6-tetra-isopropyl-diphenyl-carbo-diimide and 0.2% 4,4-dimethylbenzyldiphenylamine E oil wit-h 1% 2,6,2,6-tetra-isopropyl-diphenyl-carbodiimide and 0.2% 8-hydroxyquinoline F oil with 0.2% 4,4-dimethylbenzyldiphenylamine and 0.2% 8-hydroxyquinoline G oil with 1% 2,6,2',6-tetra-isopropyl-diphenyl-carbodiimide, 0.2% '4,4-dime-thylbenzyldiphenylamine and 0.3% S-hydroxyqumohne.
  • Example 2 100 parts of a polyether oil obtained according to Example 2 of German patent specification No. 1,120,139 by polymerisation of a mixture of tetrahydrofuran, ethylene oxide and propylene oxide in the presence of formaldheydedimethyl acetate and boron trifluoride compounds of tetrahydrofuran, are mixed with 2 parts of one of the additives listed in Table II. It is apparent from the neutralisation numbers given therein and determined according to the data of Example 1 that the resistance of the oil to oxidative attacks is likewise substantially improved in this way.
  • the letters in the'following table have the meaning:
  • a oil without additive B oil with 2% di-n-butyl carbodiimide C oil with 2% di-cyclohexyl-carbodiimide D oil with 2%, 2,6-2,6'-tetraethyl-4,4'-dirnethyl-diphenylcarbodiimide E oil with 2% 2,6,2,6-tetraethyl-diphenyl-carbodiimide F oil with 2% 2,6,2,6-tetra-isopropyl-diphenyl-carbodiimide TABLE II Duration of the Neutralisation numbers oxidative action in hours A B O D E F 0.00 0.00 0.01 0.01 0.01 0. 03 0. 0. 0. 0O 0. 01 0 01 0. 03 0. 00 0, 00 0.01 0.
  • a lubricating composition comprising (a) an oil base selected from the group consisting of a mineral oid and a synthetic polyether containing (CH -O- groups and (b) an oxidation-inhibiting amount of a member selected from the group consisting of an aliphatic monocarbodiimide, aliphatic polycarbodiimide, aromatic monocarbodiimide and aromatic polycarbodiimide.
  • a lubricating composition of claim 1 wherein the carbodiimide is a member selected from the group consisting of di-isopropyl-carbodiimide, di-n-butyl-carbodiimide, methyl-tert.-butyl-carbodiimide, dicyclohexyl-carbodiimide, diphenyl-carbodiimide, di-p-tolyl-carbodiimide, and 4,4-didodecyl-diphenyl-carbodiimide, 2,2-diethyl-diphenyl-carbodiirnide, 2,2'-di-isopropyl-diphenyl carbodiimide, 2,2-diethoxy-diphenyl-carbodiimide, 2,6,2,6'-tetraethyl diphenyl carbodiimide, 2,6,2,6-tetraisopropyl-diphenylcarbodiirnide, 2,6,2,6'-tetraeth
  • a lubricating composition of claim 1 containing an effective amount of an antioxidant selected from the group consisting of diphenylamine and hydroxy quinoline.
  • a lubricating composition of claim 2 containing about l-2% carbodiimide by weight of lubricant.

Description

United States Patent ()fiice 3,346,496 Patented Oct. 10, 1967 The present invention relates to lubricant additives; more particularly it concerns lubricant additives which consist essentially of carbodiimides.
The carbodiimides to be used as lubricant additives may be monoor poly-carbodiimides and may belong to the aliphatic, cycloaliphatic or aromatic series. Examples of monocarbodiimides are the following: di-isopropyl-carbodiimide, di-n-butyl-carbodiimide, methyl-tert.-butyl-carbodiimide, dicyclohexyl carbodiimide, diphenyl-carbodiimide, di-p-tolyl-carbodiimide and 4,4'-didodecyl-diphenyl-carbodiimide. Of special advantage are diphenyl-monocarbodiimides which carry in the phenyl radicals in orthoposition to the carbodiimide group substituents, e.g. alkyl, alkoxy, aryl and aralkyl radicals, such as 2,2'-diethyl-diphenyl carbodiimide, 2,2'-di-is0propyl-diphenylcarbodiimide, 2,2'-diethoxy-diphenyl-carbodiimide, 2,'6,2,6-tetraethyl 'cliphenyl-carbodiimide, 2,6,2',6'-tetraisopropyl-diphenyl-carbodiimide, 2,6,2,6'-tetraethyl-3,3-dichloro-diphenyl-carbodiimide, 2,2-diethyl-6,6'-dichloro-diphenylcarbodiimide, 2,6,2,6'-tetra-isobutyl-3,3-dinitro-diphenylcarbodiimide and 2,4,6,2',4,6-hexaisopropyl-diphenylcarbodiimide. Suitable polycarbodiimides are, for example, tetramethylene-w,w'-bis(tert.-butyl-carbodiimide), hexamethylene-w,w'-bis-(tert.-butyl-carbodiimide), tetrarnethylene-w,w'-bis-(phenyl-carbodiimide) and those compounds which may be obtained by heating aromatic polyisocyanates such as 1,3-di-isOpropyl-phenylene-2,4di-is cyanate, 1-methyl-3,5-diethyl-phenylene-2,4-diisocyanate and 3,5,3,5-tetra-isopropyl-diphenylmethane-4,4-di-isocyanate, in the presence of tertiary amines, basically reacting metal compounds, carboxylic acid metal salts or nonbasic organometal compounds at a temperature of at least 120 C., according to the process of German Patent No. 1,156,401.
With the aid of carbodiimides it is possible to improve substantially lubricants of a great variety of types, in particular their resistance to oxidative attacks. This applies in the first instance to lubricants which are produced from mineral oils, but also to lubricating oils of synthetic origin which are polyethers or polyether esters, but especially to lubricating oils based on synthetic polyethers or polyether esters which contain -(CH O groups alternating several times with one another or with other alkyleneO groups and which are described in German Patent No. 1,071,872. The carbodiimides are, at the same time, also efiective as protective agents against corrosion and are, moreover, capable of keeping the decomposition products formed during the lubricating process in solution. The amounts of carbodiimides required in each case can be easily determined in preliminary experiments; in general, additives of 1 to 2 percent by weight, referred to the lubricant, have proved to be sufiicient.
It is noteworthy that the lubricant additives to be used according to the present invention are compatible with other lubricant additives, e.g. with detergents, agents for increasing the resistance of the lubricating film, and also agents for improving the solidification point and the viscosity. An especially advantageous embodiment of the present invention consists in that the carbodiimides can be added to the lubricants in combination with diphenylamines known as antioxidants, such as 4,4'-di-(methylbenzyl)-diphenylamine, and/ or hydroxyquinolines such as S-hydroxyquinoline. Thus, surprisingly, a synergistic effect is achieved. The following examples serve to illustrate the invention without, however, limiting its scope; the parts given are parts by weight.
Example 1 100 parts of a naphthene-basic mineral oil are mixed with 1 part of 2,6,2,6'-tetra-is0propyl-diphenyl-carbodiimide. The resistance of the mineral oil to oxidative attacks is thus substantially improved; the action of the carbodiimide used is further increased by the addition of 0.2 part 4,4'-('dimethyl-benzyl)-diphenylamine and/or 8-hydroxyquinoline. This is evident from appropriate comparative experiments, the results of which are given in Table I, where the neutralisation numbers (mg. KOH/g. oil) of the oils mixed with the various additives are listed after oxidative action.
In the table the letters have the following significance:
A oil without additive B oil with 1% 2,6,2,6 '-tetra-isopropyl-diphenyl-carbodiimide C oil with 0.2% 4,4'-dimethylbenzyldiphenylamine D oil with 1% 2,6,2,6-tetra-isopropyl-diphenyl-carbo-diimide and 0.2% 4,4-dimethylbenzyldiphenylamine E oil wit-h 1% 2,6,2,6-tetra-isopropyl-diphenyl-carbodiimide and 0.2% 8-hydroxyquinoline F oil with 0.2% 4,4-dimethylbenzyldiphenylamine and 0.2% 8-hydroxyquinoline G oil with 1% 2,6,2',6-tetra-isopropyl-diphenyl-carbodiimide, 0.2% '4,4-dime-thylbenzyldiphenylamine and 0.3% S-hydroxyqumohne.
TABLE I Duration of the N eutralisation numbers oxidative action in hours A B C D E F G The comparative experiments were carried out according to the instruction of ASTM-oxidlising test D 943-54: 300 ml. of the oil to be tested were filled, together with 60 ml. distilled water, into a 60 cm.-high glass cylinder of 4.5 cm. diameter, and iron and copper spirals were introduced into the oil/ water mixture in accordance with the conditions prevailing in the lubricating processes. Three litres oxygen per hour were then blown at C. through the oil/ water mixture via a tube which extended almost to the bottom of the test cylinder. At specified time intervals, 10 ml. of the oil were withdrawn to determine the neutralisation number. When the neutralisation number reached a value above 2 or when the duration of the oxidative action amounted to 1000 hours, the test was interrupted.
Example 2 100 parts of a polyether oil obtained according to Example 2 of German patent specification No. 1,120,139 by polymerisation of a mixture of tetrahydrofuran, ethylene oxide and propylene oxide in the presence of formaldheydedimethyl acetate and boron trifluoride compounds of tetrahydrofuran, are mixed with 2 parts of one of the additives listed in Table II. It is apparent from the neutralisation numbers given therein and determined according to the data of Example 1 that the resistance of the oil to oxidative attacks is likewise substantially improved in this way. The letters in the'following table have the meaning:
A oil without additive B oil with 2% di-n-butyl carbodiimide C oil with 2% di-cyclohexyl-carbodiimide D oil with 2%, 2,6-2,6'-tetraethyl-4,4'-dirnethyl-diphenylcarbodiimide E oil with 2% 2,6,2,6-tetraethyl-diphenyl-carbodiimide F oil with 2% 2,6,2,6-tetra-isopropyl-diphenyl-carbodiimide TABLE II Duration of the Neutralisation numbers oxidative action in hours A B O D E F 0.00 0.00 0.01 0.01 0. 03 0. 0. 0O 0. 01 0 01 0. 03 0. 00 0, 00 0.01 0. 01 0.03 0. 01 0. 00 0.02 0.01 0. 03 0. 06 O, 00 0. ()2 0. 01 O. 0. 0. 00 0.05 O. 01 0. 12 0.21 0.03 0. l5 0. 0-1 0. 0. 29 0. 08 0. 34 0.02 0.28 0.38 0.14 0.58 0.12 0. 3G 0. 48 0.21 0.90 0.30 0. 47 0. 53 0. 29 0.95 0. 54 0. 49 0.53 0. 39 0.95 0. 84 0. 49
We claim:
1. A lubricating composition comprising (a) an oil base selected from the group consisting of a mineral oid and a synthetic polyether containing (CH -O- groups and (b) an oxidation-inhibiting amount of a member selected from the group consisting of an aliphatic monocarbodiimide, aliphatic polycarbodiimide, aromatic monocarbodiimide and aromatic polycarbodiimide.
2. A lubricating composition of claim 1 wherein the carbodiimide is a member selected from the group consisting of di-isopropyl-carbodiimide, di-n-butyl-carbodiimide, methyl-tert.-butyl-carbodiimide, dicyclohexyl-carbodiimide, diphenyl-carbodiimide, di-p-tolyl-carbodiimide, and 4,4-didodecyl-diphenyl-carbodiimide, 2,2-diethyl-diphenyl-carbodiirnide, 2,2'-di-isopropyl-diphenyl carbodiimide, 2,2-diethoxy-diphenyl-carbodiimide, 2,6,2,6'-tetraethyl diphenyl carbodiimide, 2,6,2,6-tetraisopropyl-diphenylcarbodiirnide, 2,6,2,6'-tetraethyl-3,3-dichloro-dicarbodiirnide, 2,6,2,6-tetra-isobutyl-3,3'-dinitro diphenyl-carbodiimide, and 2,4,6,2',4',6-hexaisopropyl-diphenylcarbodiimide, tetramethylene-w,w-bis-(tert.-butyl-carbodiimide), hexamethylene-w,w' bis (tert. butyl car-bodiimide tetramethy1ene-w,w'-bis- (phenyl-carbodiimide) 3. A lubricating composition of claim 1 wherein the carbodiimide is the reaction product of a lower alkyl substituted phenylene or diphenyl methane diisocyanate in the presence of a member selected from the group consisting of a tertiary amine, a basically reacting metal compound, a carboxylic acid metal salt and a non-basic organo-metal compound, the reaction being eflected at a temperature of at least 120 C.
4. A lubricating composition of claim 1 containing an effective amount of an antioxidant selected from the group consisting of diphenylamine and hydroxy quinoline.
5. A lubricating composition of claim 2 containing about l-2% carbodiimide by weight of lubricant.
References Cited UNITED STATES PATENTS 2,298,636 10/1942 Prutton 25251.5 2,458,526 1/1949 Oberright 252--51.5 2,654,680 1-0/1953 Goppel et al 260 9 X 2,776,994 1/1957 Wolfe et al. 252-401 X 2,948,680 8/1960 Fields 25251.5 X 3,004,916 10/1961 Ertelt 252- X 3,193,522 7/1965 Neumann et al 25250 X 3,193,523 7/1965 Neumann et al. 252401 X DANIEL E. WYMAN, Primary Examiner.
P. P. GARVIN, Assistant Examiner.

Claims (1)

1. A LUBRICATING COMPOSITION COMPRISING (A) AN OIL BASE SELECTED FROM THE GROUP CONSISTING OF A MINERAL OID AND A SYNTHETIC POLYETHER CONTAINING -(CH2)4-O- GROUPS AND (B) AN OXIDATION -INHIBITING AMOUTN OF A MEMBER SELECTED FROM THE GROUP CONSISTING OF AN ALIPHATIC MONOCARBONDIIMIDE, ALIPHATIC POLYCARBODIIMIDE, AROMATIC MONOCARBODIIMIDE AND AROMATIC POLYCARBODIIMIDE.
US455606A 1964-06-16 1965-05-13 Lubricants containing carbodiimides as antioxidants Expired - Lifetime US3346496A (en)

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DEF43191A DE1243811B (en) 1964-06-16 1964-06-16 Lubricant additives

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Cited By (21)

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US3505225A (en) * 1966-04-07 1970-04-07 Uniroyal Inc Derivatives of diphenylamine and the phenylnaphthylamines as antioxidants and as synergists with dialkyl 3,3'-thiodipropionates
US3666716A (en) * 1966-04-07 1972-05-30 Uniroyal Inc Derivatives of diphenylamine and the phenylnaphthylamines as antioxidants and as synergists with dialkyl 3,3{40 -thiodipropionates
US3944492A (en) * 1966-04-07 1976-03-16 Uniroyal, Inc. Lubricant compositions containing N-substituted naphthylamines as antioxidants
US4202784A (en) * 1979-04-09 1980-05-13 Standard Oil Company (Indiana) Tertiary carbinamine modified mannich compositions and lubricants containing same
US4346015A (en) * 1979-02-21 1982-08-24 Union Carbide Corporation Method of improving antiwear properties of high temperature hydrocarbon compositions
US4392968A (en) * 1980-08-13 1983-07-12 Nippon Oil Company, Limited Metal deactivator and composition containing same
US4467395A (en) * 1983-02-25 1984-08-21 Sprague Electric Company AC Metallized capacitor and impregnant therefor
EP0647701A1 (en) * 1993-03-25 1995-04-12 Asahi Denka Kogyo Kabushiki Kaisha Refrigerator lubricant and refrigerant composition containing the same
US5614483A (en) * 1994-10-05 1997-03-25 Rhein Chemie Rheinau Gmbh Stabilized lubricant base material
EP0992571A1 (en) * 1998-10-09 2000-04-12 Exxon Research And Engineering Company Lubricating oils of enhanced oxidation stability
WO2000022071A1 (en) * 1998-10-09 2000-04-20 Exxon Research And Engineering Company Polar oil based industrial oils with enhanced sludge performance
US6235687B1 (en) 1998-10-09 2001-05-22 Exxon Research And Engineering Company Method for producing lubrication oils possessing anti rust properties containing acidic anti rust additive and acid scavengers
GB2416172A (en) * 2004-07-13 2006-01-18 Alan Edwin Jemmett Rapeseed oil lubricant
US20060122077A1 (en) * 2004-12-03 2006-06-08 Bruce Wilburn Compositions comprising at least one carbodiimide
US20060122078A1 (en) * 2004-12-03 2006-06-08 Bruce Wilburn Compositions comprising at least one carbodiimide
EP2067844A1 (en) * 2006-09-29 2009-06-10 Idemitsu Kosan Co., Ltd. Lubricant for compression refrigerating machine and refrigerating apparatus using the same
GB2468750A (en) * 2009-03-21 2010-09-22 Russell Taylor Use of metal ion chelating agents to improve the performance of IC engines
WO2014161088A1 (en) 2013-04-02 2014-10-09 Brasscorp Limited Improved neutralization and removal of acids in hvac systems through the use of drying agents
WO2014180833A1 (en) * 2013-05-07 2014-11-13 Rhein Chemie Rheinau Gmbh Methods for producing oil formulations by means of certain carbodiimides
CN109181833A (en) * 2018-10-15 2019-01-11 山东奇士登润滑科技有限公司 A kind of Oil Film of Bearing Oil and preparation method thereof
FR3127952A1 (en) 2021-10-11 2023-04-14 Totalenergies Marketing Services Carbodiimide as an additive in lubricants for powertrains to improve compatibility with elastomers

Families Citing this family (1)

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FR1472132A (en) * 1965-12-27 1967-03-10 Rhone Poulenc Sa Manufacturing process of bis (4-phenylisopropylidene-phenyl) amine

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US2298636A (en) * 1939-10-04 1942-10-13 Lubri Zol Corp Lubricating composition
US2458526A (en) * 1945-07-06 1949-01-11 Socony Vacuum Oil Co Inc Mineral oil composition
US2654680A (en) * 1948-05-18 1953-10-06 Shell Dev Method for increasing stability of rubbery polymer reaction products and resulting compositions
US2776994A (en) * 1954-03-03 1957-01-08 Goodrich Co B F Preparation of a solid diphenylamine antioxidant
US2948680A (en) * 1957-03-15 1960-08-09 Standard Oil Co Lubricant compositions
US3004916A (en) * 1957-12-02 1961-10-17 Exxon Research Engineering Co Lubricating oil
US3193522A (en) * 1960-12-02 1965-07-06 Bayer Ag Stabilization of polyesters with polycarbodiimide
US3193523A (en) * 1960-12-31 1965-07-06 Bayer Ag Stabilization of polyesters with substituted carbodiimides

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Publication number Priority date Publication date Assignee Title
US2298636A (en) * 1939-10-04 1942-10-13 Lubri Zol Corp Lubricating composition
US2458526A (en) * 1945-07-06 1949-01-11 Socony Vacuum Oil Co Inc Mineral oil composition
US2654680A (en) * 1948-05-18 1953-10-06 Shell Dev Method for increasing stability of rubbery polymer reaction products and resulting compositions
US2776994A (en) * 1954-03-03 1957-01-08 Goodrich Co B F Preparation of a solid diphenylamine antioxidant
US2948680A (en) * 1957-03-15 1960-08-09 Standard Oil Co Lubricant compositions
US3004916A (en) * 1957-12-02 1961-10-17 Exxon Research Engineering Co Lubricating oil
US3193522A (en) * 1960-12-02 1965-07-06 Bayer Ag Stabilization of polyesters with polycarbodiimide
US3193523A (en) * 1960-12-31 1965-07-06 Bayer Ag Stabilization of polyesters with substituted carbodiimides

Cited By (34)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3505225A (en) * 1966-04-07 1970-04-07 Uniroyal Inc Derivatives of diphenylamine and the phenylnaphthylamines as antioxidants and as synergists with dialkyl 3,3'-thiodipropionates
US3666716A (en) * 1966-04-07 1972-05-30 Uniroyal Inc Derivatives of diphenylamine and the phenylnaphthylamines as antioxidants and as synergists with dialkyl 3,3{40 -thiodipropionates
US3944492A (en) * 1966-04-07 1976-03-16 Uniroyal, Inc. Lubricant compositions containing N-substituted naphthylamines as antioxidants
US4346015A (en) * 1979-02-21 1982-08-24 Union Carbide Corporation Method of improving antiwear properties of high temperature hydrocarbon compositions
US4202784A (en) * 1979-04-09 1980-05-13 Standard Oil Company (Indiana) Tertiary carbinamine modified mannich compositions and lubricants containing same
US4392968A (en) * 1980-08-13 1983-07-12 Nippon Oil Company, Limited Metal deactivator and composition containing same
US4467395A (en) * 1983-02-25 1984-08-21 Sprague Electric Company AC Metallized capacitor and impregnant therefor
EP0647701A4 (en) * 1993-03-25 1995-11-15 Asahi Denka Kogyo Kk Refrigerator lubricant and refrigerant composition containing the same.
EP0647701A1 (en) * 1993-03-25 1995-04-12 Asahi Denka Kogyo Kabushiki Kaisha Refrigerator lubricant and refrigerant composition containing the same
US5614483A (en) * 1994-10-05 1997-03-25 Rhein Chemie Rheinau Gmbh Stabilized lubricant base material
EP0992571A1 (en) * 1998-10-09 2000-04-12 Exxon Research And Engineering Company Lubricating oils of enhanced oxidation stability
WO2000022071A1 (en) * 1998-10-09 2000-04-20 Exxon Research And Engineering Company Polar oil based industrial oils with enhanced sludge performance
US6143702A (en) * 1998-10-09 2000-11-07 Exxon Research And Engineering Company Lubricating oils of enhanced oxidation stability containing n-phenyl-naphthyl amines, or substituted derivatives of n-phenyl naphthyl amine and carbodiimide acid scavengers
US6235687B1 (en) 1998-10-09 2001-05-22 Exxon Research And Engineering Company Method for producing lubrication oils possessing anti rust properties containing acidic anti rust additive and acid scavengers
US6750182B1 (en) 1998-10-09 2004-06-15 Exxonmobil Research And Engineering Company Polar oil based industrial oils with enhanced sludge performance
GB2416172B (en) * 2004-07-13 2009-04-22 Alan Edwin Jemmett Rapeseed oil lubricant
GB2416172A (en) * 2004-07-13 2006-01-18 Alan Edwin Jemmett Rapeseed oil lubricant
US20060122077A1 (en) * 2004-12-03 2006-06-08 Bruce Wilburn Compositions comprising at least one carbodiimide
US20060122078A1 (en) * 2004-12-03 2006-06-08 Bruce Wilburn Compositions comprising at least one carbodiimide
US7456137B2 (en) * 2004-12-03 2008-11-25 Afton Chemical Corporation Compositions comprising at least one carbodiimide
US8916060B2 (en) 2006-09-29 2014-12-23 Idemitsu Kosan Co., Ltd. Lubricant for compression refrigerating machine and refrigerating apparatus using the same
EP2067844A1 (en) * 2006-09-29 2009-06-10 Idemitsu Kosan Co., Ltd. Lubricant for compression refrigerating machine and refrigerating apparatus using the same
US20100005830A1 (en) * 2006-09-29 2010-01-14 Idemitsu Kosan Co., Ltd Lubricant for compression refrigerating machine and refrigerating apparatus using the same
EP2067844A4 (en) * 2006-09-29 2011-05-04 Idemitsu Kosan Co Lubricant for compression refrigerating machine and refrigerating apparatus using the same
GB2468750A (en) * 2009-03-21 2010-09-22 Russell Taylor Use of metal ion chelating agents to improve the performance of IC engines
WO2014161088A1 (en) 2013-04-02 2014-10-09 Brasscorp Limited Improved neutralization and removal of acids in hvac systems through the use of drying agents
US10203138B2 (en) 2013-04-02 2019-02-12 Alltemp Products Company Limited Neutralization and removal of acids in HVAC systems through the use of drying agents
WO2014180833A1 (en) * 2013-05-07 2014-11-13 Rhein Chemie Rheinau Gmbh Methods for producing oil formulations by means of certain carbodiimides
JP2016520691A (en) * 2013-05-07 2016-07-14 ライン・ケミー・ライノー・ゲーエムベーハー Method for preparing oil blends using specific carbodiimides
US9464256B2 (en) * 2013-05-07 2016-10-11 Rhein Chemie Rheinau Gmbh Methods for producing oil formulations by means of certain carbodiimides
CN109181833A (en) * 2018-10-15 2019-01-11 山东奇士登润滑科技有限公司 A kind of Oil Film of Bearing Oil and preparation method thereof
CN109181833B (en) * 2018-10-15 2021-06-11 山东奇士登润滑科技有限公司 Oil film bearing oil and preparation method thereof
FR3127952A1 (en) 2021-10-11 2023-04-14 Totalenergies Marketing Services Carbodiimide as an additive in lubricants for powertrains to improve compatibility with elastomers
WO2023061899A1 (en) 2021-10-11 2023-04-20 Totalenergies Onetech Carbodiimide for use as an additive in lubricants intended for drive device systems for improved elastomer compatibility

Also Published As

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DE1243811B (en) 1967-07-06
NL6507710A (en) 1965-12-17
BE665202A (en) 1965-10-01
GB1049618A (en) 1966-11-30
FR1437094A (en) 1966-04-29
NL144982B (en) 1975-02-17

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