US3844963A - Lubricants - Google Patents

Lubricants Download PDF

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Publication number
US3844963A
US3844963A US00269205A US26920572A US3844963A US 3844963 A US3844963 A US 3844963A US 00269205 A US00269205 A US 00269205A US 26920572 A US26920572 A US 26920572A US 3844963 A US3844963 A US 3844963A
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United States
Prior art keywords
dithiophosphoric acid
group
hour
isocyanate
mono
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US00269205A
Inventor
J Elliott
G Jayne
P Folliard
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Cooper E & Co Ltd gb
Edwin Cooper and Co Ltd
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Edwin Cooper and Co Ltd
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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
    • C10M137/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing phosphorus
    • C10M137/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing phosphorus having no phosphorus-to-carbon bond
    • C10M137/04—Phosphate esters
    • C10M137/10—Thio derivatives
    • C10M137/105—Thio derivatives not containing metal
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/06—Phosphorus compounds without P—C bonds
    • C07F9/16—Esters of thiophosphoric acids or thiophosphorous acids
    • C07F9/165—Esters of thiophosphoric acids
    • C07F9/1654—Compounds containing the structure P(=X)n-X-acyl, P(=X)n-X-heteroatom, P(=X)n-X-CN (X = O, S, Se; n = 0, 1)
    • C07F9/1656—Compounds containing the structure P(=X)n-X-C(=X)- (X = O, S, Se; n = 0, 1)
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2201/00—Inorganic compounds or elements as ingredients in lubricant compositions
    • C10M2201/06—Metal compounds
    • C10M2201/062—Oxides; Hydroxides; Carbonates or bicarbonates
    • 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
    • C10M2203/108—Residual fractions, e.g. bright stocks
    • C—CHEMISTRY; METALLURGY
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    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/02—Hydroxy compounds
    • C10M2207/023—Hydroxy compounds having hydroxy groups bound to carbon atoms of six-membered aromatic rings
    • C—CHEMISTRY; METALLURGY
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    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/02—Hydroxy compounds
    • C10M2207/023—Hydroxy compounds having hydroxy groups bound to carbon atoms of six-membered aromatic rings
    • C10M2207/024—Hydroxy compounds having hydroxy groups bound to carbon atoms of six-membered aromatic rings having at least two phenol groups but no condensed ring
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    • C10M2207/02—Hydroxy compounds
    • C10M2207/023—Hydroxy compounds having hydroxy groups bound to carbon atoms of six-membered aromatic rings
    • C10M2207/027—Neutral salts thereof
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    • C10M2207/02—Hydroxy compounds
    • C10M2207/023—Hydroxy compounds having hydroxy groups bound to carbon atoms of six-membered aromatic rings
    • C10M2207/028—Overbased salts thereof
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    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/10—Carboxylix acids; Neutral salts thereof
    • C10M2207/12—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms
    • C10M2207/121—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of seven or less carbon atoms
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    • C10M2207/10—Carboxylix acids; Neutral salts thereof
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    • C10M2207/122—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of seven or less carbon atoms monocarboxylic
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    • C10M2207/10—Carboxylix acids; Neutral salts thereof
    • C10M2207/12—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms
    • C10M2207/121—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of seven or less carbon atoms
    • C10M2207/123—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of seven or less carbon atoms polycarboxylic
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    • C10M2207/10—Carboxylix acids; Neutral salts thereof
    • C10M2207/12—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms
    • C10M2207/129—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of thirty or more carbon atoms
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    • C10M2207/10—Carboxylix acids; Neutral salts thereof
    • C10M2207/14—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to carbon atoms of six-membered aromatic rings
    • C10M2207/144—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to carbon atoms of six-membered aromatic rings containing hydroxy groups
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    • C10M2207/146—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to carbon atoms of six-membered aromatic rings having carboxyl groups bound to carbon atoms of six-membeered aromatic rings having a hydrocarbon substituent of thirty or more carbon atoms
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    • C10M2207/10—Carboxylix acids; Neutral salts thereof
    • C10M2207/16—Naphthenic acids
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    • C10M2207/22—Acids obtained from polymerised unsaturated acids
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    • C10M2207/262—Overbased carboxylic acid salts derived from hydroxy substituted aromatic acids, e.g. salicylates
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    • C10M2207/281—Esters of (cyclo)aliphatic monocarboxylic acids
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    • C10M2207/282—Esters of (cyclo)aliphatic oolycarboxylic acids
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    • C10M2207/286—Esters of polymerised unsaturated acids
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    • C10M2207/302—Complex esters, i.e. compounds containing at leasst three esterified carboxyl groups and derived from the combination of at least three different types of the following five types of compounds: monohydroxyl compounds, polyhydroxy xompounds, monocarboxylic acids, polycarboxylic acids or hydroxy carboxylic acids derived from the combination of monocarboxylic acids, dicarboxylic acids and dihydroxy compounds only and having no free hydroxy or carboxyl groups
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Definitions

  • a lubricant composition comprises a major amount of lubricating oil and a minor amount of one or more oilsoluble dithiophosphoric acid derivatives having the general formula:
  • R is a monoor di-valent aliphatic or aromatic group
  • X is an oxygen or sulphur atom
  • R is an alkyl group
  • R and R are the same or different and are alkyl, alkaryl, aryl or aralkyl groups or alkenyl and n is 0 when R is a monovalent group or is 1 when R is a divalent group.
  • dithiophosphoric acid derivatives certain of v which are novel compounds, function as antioxidants, load carrying and antiwear additives in the lubricant compositions.
  • This invention relates to lubricants and in particular to lubricants containing S-carbamoyl dithiophosphates.
  • Ar is arylene of from 6 to 12 carbon atoms and R is a hydrocarbyl group, substantially free of aliphatic unsaturation, having from 12 to 30 carbon atoms.
  • dithiophosphate lubricant additives in addition to possessing antioxidant, loadcarrying and antiwear properties, should not be unduly prone to form deposits in oil solution at the elevated temperatures at which internal combustion engines are normally operated. e.g., up to 130C.
  • the present invention provides lubricants containing ash-free dithiophosphoric acid derivatives, some of which are novel compounds, having a reduced tendency to form deposits composed of oil-insoluble diisothiocyanate decomposition products.
  • the present invention provides a lubricant composition
  • a lubricant composition comprising a major amount of lubricating oil and a minor amount of one or more oilsoluble dithiophosphoric acid derivatives having the general formula:
  • R 's" A wherein R is a monoor di-valent aliphatic or aromatic group; X is an oxygen or sulphur atom; R is an alkyl group; R and R are the same or different and are alkyl, alkaryl, aryl or aralkyl groups or alkenyl and n is 0 when R is a monovalent group or is 1 when R is a divalent group.
  • the additives of the present invention may contain as a contaminant. a small proportion of isothiocyanate decomposition products.
  • the groups R and R are preferably alkyl, alkaryl or aralkyl groups. and may contain from l to 30, preferably 4 to l8, carbon atoms.
  • the group R may contain from l to 30. preferably 2 to 22. more preferably 4 to l3. carbon atoms.
  • the group R is preferably a monovalent alkyl group containing from 1 to 18 carbon atoms or a di-valent aryl'group, optionally bearing one or more alkyl substituents, which contains from 6 to 24 carbon atoms. a
  • the dithiophosphoric acid derivatives employed in the lubricants of the present invention may be prepared by reacting an isocyanate compound, as more fully described hereinaftenwith a dithiophosphoric acid.
  • the dithiophosphoric acid'starting materials may be prepared by reaction of 1 mole of phosphorus pentasulphide with 4 moles of an alcohol ormixture of alcohols, a phenol or mixture of phenols or a mixture of one or more alcohols and one or more phenols in accordance with techniques well-known in the preparation of the zinc salts of 0,-0-dihydrocarbyl dithiophosphoric acids hereinbefore described.
  • the nature of the alcohol and/or phenol employed will determine the nature of the groups'R and R in the additives of the present invention. Examples of alcohols which may be used include:
  • ethanol n-propanol isopropanol n-butanol isobutanol amyl alcohol including mixed amyl alcohols mixtures of alcohols, derived from the OX0 process decanol dodecanol lauryl alcohol Suitable phenols include:
  • Suitable mixtures of alcohols and phenols include:
  • the isocyanate compound which may be employed in the preparation of the additives can be a monoisocyanate, preferably an aliphatic mono-isocyanate, of the formula:
  • Suitable mono-isocyanates which may be used to prepare S-carbamoyl dithiophosphates which may be used in the present invention include:
  • the isocyanate compound can have the formula:
  • lsocyanates of the latter formula may be prepared by reacting one of the isocyanate groups of a di-isocyanate with an alcohol or mercaptan.
  • Suitable di-isocyanates include toluene 2,4, diisocyanate, which is particularly preferred.
  • di-isocyanates are:
  • Compounds which may be reacted with the diisocyanate include:
  • the temperature at which the additives of the present invention are prepared may be varied according to the preparative route chosen. In order to obtain the optimum antioxidant performance, load-carrying ability and to minimise deposit formation at elevated temperatures it is preferred to carry out the reaction with the dithiophosphoric acid at about 75 80C., although temperatures of up to 100C. or as low as ambient temperature may be employed. if desired.
  • Each of the reactions carried out in the preparation of the additives is conventiently carried out at atmospheric pressure. However, any or all of the reactions may be carried out, if desired, at pressures above or below atmospheric.
  • the lubricants of the present invention may contain from 0.1 to preferably from 0.5 to 5%, by weight of the dithiophosphoric acid derivatives.
  • the lubricants may also contain other additives of the type conventionally used in lubricants, especially ash-free additives.
  • additives include antioxidants and antiwear additives (additional to the dithiophosphoric acid derivatives) and corrosion inhibitors, detergents, dispersants, viscosity index improvers. extreme pressure additives or any combination thereof.
  • Suitable additional antioxidants are phenothiazine, optionally substituted on one or both benzene nuclei and/or the nitrogen atom, a hindered phenol or a hindered bis-phenol or a secondary amine having two aromatic nuclei attached to the nitrogen atom.
  • the additional antioxidant is a secondary amine having two aromatic nuclei attached to the nitrogen atom, in which one or both of the aromatic nuclei bear one or more alkyl groups, particularly alkyl groups containing from 4 to 12, more preferably 8 or 9, carbon atoms.
  • Examples of such amines are monooctyl phenyl-a-naphthylamines and mono-octyl phenyl-B-naphthylamines, particularly N-p-t-octyl phenyl-a-naphthylamine and N-p-t-octyl phenyl-finaphthylamine; and mono-nonyl phenyl-anaphthylamines and mono-nonyl phenyl-B- naphthylamines.
  • amines are diphenylamine and monoor di-alkyl diphenylamines, particular examples being di-octyl and di-nonyl diphenylamines, especially the p-p isomers. These secondary amines may be used in an amount of from 0.1% by weight, preferably 0.2% to 5% by weight.
  • ash-free antioxidants which may be used include the trithiopyrophosphate additives described in British Pat. No. 1,254,554, and in German Offenlegungsschrift No. 2,162,180 and copending United States application Ser. No. 252,254 filed May 11, 1972.
  • Suitable corrosion inhibitors include benzotriazole or a derivative thereof, an aliphatic carboxylic acid, a dicarboxylic acid, for example, dodecenyl succinic acid, mercaptobenzothiazole and benzothiazole disulphide.
  • Suitable detergents include an alkaline earth metal petroleum or alkyl benzene sulphonate, carboxylate, salicylate or naphthenate, any of which may be overbased with an alkaline earth metal carbonate.
  • Other suitable detergents, which may also be overbased, include a phosphosulphurised hydrocarbon and an alkyl phenol which has been neutralised by an alkaline earth metal base.
  • a suitable dispersant is a long chain hydrocarbon substituted by a polyamine group attached thereto either directly or through an amide or imide link, as described in British Pat. Nos. 1,068,235 and 1,121,641.
  • a typical viscosity index improver which may be used in this invention is a copolymer of a mixture of monomers, which monomers are esters of acrylic or methacrylic acid.
  • Other unsaturated monomers such as N- vinyl pyrrolidone, diethylamino-ethyl methacrylate or fumaric acid may be included in the mixture to give viscosity index improvers having dispersant properties.
  • dithiophosphoric acid derivatives which can be diluted with additional lubricating oil before being used.
  • these more concentrated solutions may be oil concentrates or additive packages, i.e., may be, respectively concentrated solutions of one or more dithiophosphoric acid derivatives or concentrated solutions of mixtures of one or more dithiophosphoric acid derivatives and one or more known additives.
  • an oil concentrate or additive package comprising from 10% to more preferably 20% to 50%, by weight of a lubricating oil having dissolved therein from 90% to 30%, more preferably to 50%, by weight of one or more of the dithiophosphoric acid derivatives, optionally together with one or more known additives.
  • the lubricating oil employed in the lubricants, oil concentrates and additive packages of the present invention may be a mineral oil of lubricating viscosity of well-known type.
  • a synthetic ester-based oil may be used as the lubricating oil. Suitable synthetic ester oils are described in British Pat. Nos. 930,136 and 1,205,177.
  • dithiophosphoric acid derivatives employed in the lubricants are novel compounds.
  • the present invention therefore includes in another aspect novel dithiophosphoric acid derivatives suitable for use as lubricant additives, having the general formula:
  • R, R R as a di-valent group, R and X are as hereinbefore defined.
  • R, R R as a di-valent group, R and X are as hereinbefore defined.
  • the present invention further provides a process for the preparation of a dithiophosphoric acid derivative, which process comprises reacting a compound of the formula:
  • the invention also includes a dithiophosphoric acid derivatives when produced by either of the above processes.
  • EXAMPLE 1 Ethyl isocyanate (13.8g. 0.2m) was added dropwise to stirred di-tridecyl dithiophosphoric acid (110g.
  • EXAMPLE a Toluene di-isocyanate 174g, 1.0m) was heated to approximately 105C. and 0,0-di-isobutyl dithiophosphoric acid (250g. 1.0m) run in over /4 hour and left to react for a further 2 /4 hours at 105C.
  • Tridecanol (40.0g., 0.2m.) was added to toluene diisocyanate (34.8g.. 0.2m.) over /2 hour at a temperature of 7080C. and the product stirred for a further V2 hour.
  • To the product was then added 0,0'-di-isobutyl dithiophosphoric acid (55.6g., 0.2m.) over /4 hour followed by a further 4.0g. (10%) of tridecanol and the reaction continued for a further one hour to yield 1 19g. (95% of an olive green liquid containing 5.00%? (theory 5.04%
  • EXAMPLE 9 An 0,0-dialkyl dithiophosphoric acid was prepared by reaction of P 5 with Alfol 20-22 (a commercially available mixture of alcohols containing 20-22 carbon atoms). To toluene di-isocyanate (34.8g., 0.2m.) was added, in bulk. 2-ethylhexanol (26g, 0.2m.), causing an exotherm. To the product was added the 0,0'-di- Alfol 20-22 dithiophosphoric acid (150g.,0.2m.), after melting. causing the temperature to rise to 50C. The total addition time of the dithiophosphoric acid was hour. after which the reaction was continued for a further 1 /2 hours to yield 205g. (97.5%) of a grey/green solid containing 2.77%P (theory 2.93%).
  • EXAMPLE 10 a. lsobutanol (74.0g., 1.0m.) was added dropwise to toluene di-isocyanate 174g, 1.0m.) over 1: hour, during which time the initial temperature of 30C. rose to C. due to the strong exotherm. The reaction was continued, with stirring, for a further one hour.
  • EXAMPLE 12 EXAMPLE l3 lsobutanol l4.8g., 0.2m. was added in bulk to toluene di-isocyanate (69.6g., 0.4m.) and reacted for one hour at 30-45C. 0,0-di-2-ethylhexyl dithiophosphoric acid (76.8g., 0.2m.) was added dropwise over 1 hour at 30C. and reaction contined for /2 hour. To 129g. of the resulting product was added.
  • Example 17 The procedure of Example 16 was repeated using toluene di-isocyanate (69.6g., 0.4m.) and Alfol 6 (40.8g., 0.4m.) (with a strong exotherm to 80C.), and 0,0-ditridecyl dithiophosphoric acid (216g, 0.4m.) to yield 32 l g. (98.5%) of a light green viscous liquid containing 3.95%P (theory 4.03%).
  • Example 18 The procedure of Example 16 was repeated using toluene (ii-isocyanate (69.6g., 0.4m.), 2-ethylhexanol (520g, 0.4m.), and 0,0-di-tridecyl dithiophosphoric acid (216g, 0.4m.) to yield 327g. (98%) ofa very light green mobile liquid containing 3.74%? (theory 3.89%).
  • Example 19 The procedure of Example 16 was repeated using toluene di-isocyanate (696g, 0.4m.) 3,5,5- trimethylhexanol (57.6g., 0.4m.), and 0,0-di-isobutyl dithiophosphoric acid (106.8g., 0.4m.) to yield 21 lg. (90.5%) of a light green solid containing 5.63%? (theory 5.22%).
  • EXAMPLE 20 isodecanol (79g, 0.5m.) was added to toluene diisocyanate (87g, 0.5m.) over A hour. The initial temperature was 50C., exotherming strongly to a maximum 105C. The reaction mixture was cooled to 80C. and stirred for a further 1 1 hour. 0,0'-di-isobutyl dithiophosphoric acid 134g., 0.5m.) was then added over A hour, keeping the temperature at 7580C., and the mixture stirred for a further 14 hour, whereafter isodecanol (7.9g, was added to ensure completion of reaction. There was obtained 201g. (96%) of a light green fairly mobile liquid containing 5.3%P (theory 5.4%).
  • EXAMPLE 21 In a manner identical to Example 20, except that a dry nitrogen stream was passed through the reaction mixture to prevent moisture absorption by toluene diisocyanate, there was prepared from toluene diisocyanate (435g, 2.5m.), isodecanol (395g, 2.5m.)
  • EXAMPLE 22 This was a repetition of Example 21, identical in every respect, and the product contained 5.3%P and 12.0%S.
  • EXAMPLE 23 An 0,0'-di-P1B phenyl dithiophosphoric acid was prepared from P S and a polyisobutenyl substituted phe-' EXAMPLE 24 Phenyl isocyanate (23.8g., 0.2m.) was weighed carefully into a flask and 0,0'-di-isobutyl dithiophosphoric acid (52.6g., 0.2m.) slowly added thereto. The resulting reaction was vigorously exothermic, causing a maximum temperature of 90C. to be obtained. Stirring was continued for hour and the final product was a dark green liquid.
  • the products of a number of the preparations exemplified above were tested by means of the Timken O.K. load test in accordance with the Institute of Petroleums Test Method IP/240/69.
  • the apparatus employed comprises a roller mounted on a spindle, the roller being rotated against a seated metal block lubricated with the test blend.
  • a lever system mounted on the spindle is also mounted on the spindle, the weight being increased until the test blend fails as judged by scoring of the seated metal block.
  • the blends tested consisted of sufficient of the test additives to provide a phosphorus content of 0.072% by weight in a base oil which was 150 Solvent Neutral mineral oil having viscosities of about 33 and 5 cSt at 100F. and 210F. re spectively.
  • the base oil alone had a Timken O.K. load of 12 lbs. and the results obtained with the various test additives are as set out above in each relevant example.
  • Typical results obtained in this test with the widely used zinc 0.0-di-hydrocarbyl dithiophosphates, at 0.08% by weight phosphorus level, are 33 lbs. (hydrocarbyl mixed isobutyl and pentyl groups), 35 lbs.
  • Base Oil only 45 min. Base oil product of Example 1. 122 min. Base oil product of Example 2. 78 min. Base oil product of Example 3. 402 min. Base oil product of Example 26. 129 min. Base oil product of Example 27. 88 min.@ Base oil Additive 4. 405 min. Base oil Additive 2. 298 min. Base oil Additive 3. 82 min.@ Base oil Additive 5. 124 min.
  • Solvent Neutral mineral oil having viscositics of about 1 l0 and 11 C51. at 100F. and 210F. respectively. em 25 p.s.i. loss.
  • sintered glass crucibles had been cleaned, flushed through with acetone, dried in an oven at 100C. for about /2 hour, cooled in air and weighed.
  • each blend was poured into approximately 200ml. of heptane and the resulting mixture filtered as quickly as possible through a crucible.
  • the crucible contents were then thoroughly rinsed with clean heptane to ensure all oil was removed, then dried in the oven for about /2 hour, cooled in air and re-weighed.
  • the results obtained were expressed as the weight of precipitate collected/weight of additive in blend X 100% In this way were evaluated blends containing one of the aforesaid prior art additives and blends containing the product of Example 25, the results being as follows:
  • a composition according to claim 1 containing 1.
  • a lubricant composition consisting essentially of lubricating oil having dissolved therein from about 0.1 to 10% by weight of at least one oil-soluble dithiophosphoric acid derivative having the general formula:
  • R is selected from the group consisting of mono-valent aliphatic groups, mono-valent aromatic groups. di-valent aliphatic groups and di-valent aromatic groups;
  • X is selected from the group consisting of oxygen atoms and sulphur atoms;
  • R is an alkyl group;
  • R and R are the same or different and are selected from the group consisting of alkyl groups, alkaryl groups, aryl groups, aralkyl groups and alkenyl groups; and
  • n is 0 when R is a mono-valent group and n is I when R is a divalent group.
  • R and R are selected from the group consisting of alkyl, alkaryl and aralkyl groups containing from 4 to 18 carbon atoms.
  • R is selected from the group consisting of a mono-valent alkyl group containing from I to 18 carbon atoms and a divalent aryl group.
  • R is a divalent aryl group bearing at least one alkyl substitutent and containing from 6 to 24 carbon atoms.
  • R is selected from the group consisting of mono-valent aliphatic groups, mono-valent aromatic groups, di-valent aliphatic groups and di-valent aromatic groups
  • X is selected from the group consisting of oxygen atoms and sulphur atoms
  • R is an alkyl group
  • R and R are the same or different and are selected from the group consisting of alkyl groups, alkaryl groups, aryl groups, aralkyl groups and alkenyl groups
  • n is 0 when R is a mono-valent group and n is 1 when R is a di-valent group.

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Abstract

A lubricant composition comprises a major amount of lubricating oil and a minor amount of one or more oil-soluble dithiophosphoric acid derivatives having the general formula:

WHEREIN R3 is a mono- or di-valent aliphatic or aromatic group; X is an oxygen or sulphur atom; R4 is an alkyl group; R1 and R2 are the same or different and are alkyl, alkaryl, aryl or aralkyl groups or alkenyl and n is 0 when R3 is a monovalent group or is 1 when R3 is a divalent group. The dithiophosphoric acid derivatives, certain of which are novel compounds, function as antioxidants, load carrying and antiwear additives in the lubricant compositions.

Description

United States Patent 1 Elliott et al.
[451 Oct. 29, 1974 LUBRICANTS [73] Assignee: Edwin Cooper & Company Limited, London, England [22] Filed: July 5, 1972 [2]] Appl. No.: 269,205
[30] Foreign Application Priority Data July 6, 1971 Great Britain 31634/71 [52] US. Cl. 252/46t7, 252/400 A [51] Int. Cl C10m l/48 [58] Field of Search 252/46.7, 400 A [56] References Cited UNITED STATES PATENTS 2,648,696 8/1953 Whetstone 260/935 2,743,235 4/1956 McDermott 252/46.7 3,3l7,425 5/1967 Hasserodt et al... 252/46.7 3,446,738 5/1969 Chao et al. 252/46.7 3,537,998 ll/l970 Lowe 252/46.7
Primary Examiner-Helen M. S. Sneed Attorney, Agent, or FirmBacon & Thomas [5 7 ABSTRACT A lubricant composition comprises a major amount of lubricating oil and a minor amount of one or more oilsoluble dithiophosphoric acid derivatives having the general formula:
wherein R is a monoor di-valent aliphatic or aromatic group; X is an oxygen or sulphur atom; R is an alkyl group; R and R are the same or different and are alkyl, alkaryl, aryl or aralkyl groups or alkenyl and n is 0 when R is a monovalent group or is 1 when R is a divalent group.
The dithiophosphoric acid derivatives, certain of v which are novel compounds, function as antioxidants, load carrying and antiwear additives in the lubricant compositions.
8 Claims, No Drawings LUBRICANTS This invention relates to lubricants and in particular to lubricants containing S-carbamoyl dithiophosphates.
Many dithiophosphate compounds have been employed as additives in lubricants to reduce wear and to act as antioxidants, the most widely used additives being the zinc salts of 0,0'-dihydrocarbyl dithiophosphoric acids. These zinc salts have been widely used for many years and have proved to be very useful in formulating lubricants. Nevertheless, the zinc salts suffer from a number of disadvantages and in particular cannot be employed in ash-free lubricants since the zinc content is a source of ash. Consequently efforts have been made to prepare ash-free dithiophosphoric acid derivatives which can be employed as antioxidants, load carrying and antiwear additives.
In US. Pat. No. 3,537,998 there are described certain dithiophosphoric acid derivatives useful as antioxidant, antiwear and extreme pressure additives, which derivatives have the formula:
wherein Ar is arylene of from 6 to 12 carbon atoms and R is a hydrocarbyl group, substantially free of aliphatic unsaturation, having from 12 to 30 carbon atoms.
It is desirable that dithiophosphate lubricant additives in addition to possessing antioxidant, loadcarrying and antiwear properties, should not be unduly prone to form deposits in oil solution at the elevated temperatures at which internal combustion engines are normally operated. e.g., up to 130C.
The present invention provides lubricants containing ash-free dithiophosphoric acid derivatives, some of which are novel compounds, having a reduced tendency to form deposits composed of oil-insoluble diisothiocyanate decomposition products.
Accordingly the present invention provides a lubricant composition comprising a major amount of lubricating oil and a minor amount of one or more oilsoluble dithiophosphoric acid derivatives having the general formula:
R 's" A wherein R is a monoor di-valent aliphatic or aromatic group; X is an oxygen or sulphur atom; R is an alkyl group; R and R are the same or different and are alkyl, alkaryl, aryl or aralkyl groups or alkenyl and n is 0 when R is a monovalent group or is 1 when R is a divalent group.
The additives of the present invention may contain as a contaminant. a small proportion of isothiocyanate decomposition products.
The groups R and R are preferably alkyl, alkaryl or aralkyl groups. and may contain from l to 30, preferably 4 to l8, carbon atoms. The group R may contain from l to 30. preferably 2 to 22. more preferably 4 to l3. carbon atoms. The group R is preferably a monovalent alkyl group containing from 1 to 18 carbon atoms or a di-valent aryl'group, optionally bearing one or more alkyl substituents, which contains from 6 to 24 carbon atoms. a
lt will be understood that the carbon atom content of the groups R, R, R" and R will be selected so as to provide an oil-soluble compound.
The dithiophosphoric acid derivatives employed in the lubricants of the present invention may be prepared by reacting an isocyanate compound, as more fully described hereinaftenwith a dithiophosphoric acid. The dithiophosphoric acid'starting materials may be prepared by reaction of 1 mole of phosphorus pentasulphide with 4 moles of an alcohol ormixture of alcohols, a phenol or mixture of phenols or a mixture of one or more alcohols and one or more phenols in accordance with techniques well-known in the preparation of the zinc salts of 0,-0-dihydrocarbyl dithiophosphoric acids hereinbefore described. Thus, the nature of the alcohol and/or phenol employed will determine the nature of the groups'R and R in the additives of the present invention. Examples of alcohols which may be used include:
ethanol n-propanol isopropanol n-butanol isobutanol amyl alcohol, including mixed amyl alcohols mixtures of alcohols, derived from the OX0 process decanol dodecanol lauryl alcohol Suitable phenols include:
p-tert-butyl phenol heptyl phenol p-nonyl phenol m-pentadecyl phenol polyalkylene substituted phenols preferably derived from polypropylene, especially propylene tetramer, and polyisobutylenes having molecular weights up to 2,500.
Examples of suitable mixtures of alcohols and phenols include:
mixtures of isobutanol with mixed amyl alcohols isopropyl alcohol and l-methyl heptanol isopropyl alcohol and 2-ethyl hexanol isobutanol and 2-ethyl hexanol amyl alcohol and p-tertiary octyl phenol The dithiophosphoric acids prepared in the above described manner are reacted with the isocyanate compound.
The isocyanate compound which may be employed in the preparation of the additives can be a monoisocyanate, preferably an aliphatic mono-isocyanate, of the formula:
Suitable mono-isocyanates which may be used to prepare S-carbamoyl dithiophosphates which may be used in the present invention include:
methyl isocyanate ethyl isocyanate n-propyl isocyanate isopropyl isocyanate n-butyl isocyanate tert-butyl isocyanate octadecyl isocyanatc allyl isocyanate phenyl isocyanate Alternatively, the isocyanate compound can have the formula:
wherein R, R and X are as hereinbefore defined. lsocyanates of the latter formula may be prepared by reacting one of the isocyanate groups of a di-isocyanate with an alcohol or mercaptan.
la a further alternative preparation of the additives used in the present invention a dithiophosphoric acid is reacted with one of the isocyanate groups of a diisocyanate and the remaining isocyanate group is reacted with an alcohol or mercaptan.
Suitable di-isocyanates include toluene 2,4, diisocyanate, which is particularly preferred.
Other di-isocyanates are:
diphenyl methane di-isocyanate 3-3-dimethyl-4,4' biphenylene di-isocyanate trimethyl hexamethylene di-isocyanate hexa methylene di-isocyanate Compounds which may be reacted with the diisocyanate include:
methanol ethanol isopropanol n-butanol isobutanol amyl alcohol n-hexyl alcohol Z-ethylhexanol 3,5,5-trimethyl-hexanol isodecanol n-decanol dodecanol isotridecanol mixed straight chain alcohols sold under the trade name Alfol containing up to 22 carbon atoms, and n-dodecyl mercaptan.
The temperature at which the additives of the present invention are prepared may be varied according to the preparative route chosen. In order to obtain the optimum antioxidant performance, load-carrying ability and to minimise deposit formation at elevated temperatures it is preferred to carry out the reaction with the dithiophosphoric acid at about 75 80C., although temperatures of up to 100C. or as low as ambient temperature may be employed. if desired.
Each of the reactions carried out in the preparation of the additives is conventiently carried out at atmospheric pressure. However, any or all of the reactions may be carried out, if desired, at pressures above or below atmospheric.
The lubricants of the present invention may contain from 0.1 to preferably from 0.5 to 5%, by weight of the dithiophosphoric acid derivatives. The lubricants may also contain other additives of the type conventionally used in lubricants, especially ash-free additives. Such additives include antioxidants and antiwear additives (additional to the dithiophosphoric acid derivatives) and corrosion inhibitors, detergents, dispersants, viscosity index improvers. extreme pressure additives or any combination thereof.
Suitable additional antioxidants are phenothiazine, optionally substituted on one or both benzene nuclei and/or the nitrogen atom, a hindered phenol or a hindered bis-phenol or a secondary amine having two aromatic nuclei attached to the nitrogen atom. In one aspect of the invention the additional antioxidant is a secondary amine having two aromatic nuclei attached to the nitrogen atom, in which one or both of the aromatic nuclei bear one or more alkyl groups, particularly alkyl groups containing from 4 to 12, more preferably 8 or 9, carbon atoms. Examples of such amines are monooctyl phenyl-a-naphthylamines and mono-octyl phenyl-B-naphthylamines, particularly N-p-t-octyl phenyl-a-naphthylamine and N-p-t-octyl phenyl-finaphthylamine; and mono-nonyl phenyl-anaphthylamines and mono-nonyl phenyl-B- naphthylamines. Other amines are diphenylamine and monoor di-alkyl diphenylamines, particular examples being di-octyl and di-nonyl diphenylamines, especially the p-p isomers. These secondary amines may be used in an amount of from 0.1% by weight, preferably 0.2% to 5% by weight. Other ash-free antioxidants which may be used include the trithiopyrophosphate additives described in British Pat. No. 1,254,554, and in German Offenlegungsschrift No. 2,162,180 and copending United States application Ser. No. 252,254 filed May 11, 1972.
Suitable corrosion inhibitors include benzotriazole or a derivative thereof, an aliphatic carboxylic acid, a dicarboxylic acid, for example, dodecenyl succinic acid, mercaptobenzothiazole and benzothiazole disulphide.
Suitable detergents include an alkaline earth metal petroleum or alkyl benzene sulphonate, carboxylate, salicylate or naphthenate, any of which may be overbased with an alkaline earth metal carbonate. Other suitable detergents, which may also be overbased, include a phosphosulphurised hydrocarbon and an alkyl phenol which has been neutralised by an alkaline earth metal base.
A suitable dispersant is a long chain hydrocarbon substituted by a polyamine group attached thereto either directly or through an amide or imide link, as described in British Pat. Nos. 1,068,235 and 1,121,641.
A typical viscosity index improver which may be used in this invention is a copolymer of a mixture of monomers, which monomers are esters of acrylic or methacrylic acid. Other unsaturated monomers such as N- vinyl pyrrolidone, diethylamino-ethyl methacrylate or fumaric acid may be included in the mixture to give viscosity index improvers having dispersant properties.
In certain cases, e.g., for ease of transport, it may be desirable to prepare more concentrated solutions of the dithiophosphoric acid derivatives which can be diluted with additional lubricating oil before being used. These more concentrated solutions may be oil concentrates or additive packages, i.e., may be, respectively concentrated solutions of one or more dithiophosphoric acid derivatives or concentrated solutions of mixtures of one or more dithiophosphoric acid derivatives and one or more known additives. Accordingly, in a further embodiment of the invention there is provided an oil concentrate or additive package comprising from 10% to more preferably 20% to 50%, by weight of a lubricating oil having dissolved therein from 90% to 30%, more preferably to 50%, by weight of one or more of the dithiophosphoric acid derivatives, optionally together with one or more known additives.
The lubricating oil employed in the lubricants, oil concentrates and additive packages of the present invention may be a mineral oil of lubricating viscosity of well-known type. Alternatively, a synthetic ester-based oil may be used as the lubricating oil. Suitable synthetic ester oils are described in British Pat. Nos. 930,136 and 1,205,177.
As hereinbefore stated certain of the dithiophosphoric acid derivatives employed in the lubricants are novel compounds. The present invention therefore includes in another aspect novel dithiophosphoric acid derivatives suitable for use as lubricant additives, having the general formula:
wherein R, R R as a di-valent group, R and X are as hereinbefore defined.
1n yet another aspect of the present invention there is provided a process for the preparation of a dithiophosphoric acid derivative, which process comprises reacting an isocyanate compound of the formula:
0 0 CNR3NH ll-X-R with a compound of formula:
R 0 SH to produce a dithiophosphoric acid derivative having the general formula:
wherein R, R R as a di-valent group, R and X are as hereinbefore defined.
Moreover the present invention further provides a process for the preparation of a dithiophosphoric acid derivative, which process comprises reacting a compound of the formula:
with one of the isocyanate groups of a di-isocyanate and thereafter reacting the remaining isocyanate group with an alcohol or mercaptan.
It is to be understood that the invention also includes a dithiophosphoric acid derivatives when produced by either of the above processes.
The preparation of dithiophosphoric acid derivatives which may be used in lubricants in accordance with the present invention will now be illustrated with reference to the following non-limiting examples.
EXAMPLE 1 Ethyl isocyanate (13.8g. 0.2m) was added dropwise to stirred di-tridecyl dithiophosphoric acid (110g.
' 0.2m) over a period of about 1 hour, the temperature of the reaction mixture being maintained at -85C. After each addition an exotherm was noticed.
When the addition was complete the product was allowed to cool slowly, with stirring, to yield g. (97%) of a light green mobile liquid.
Analysis: 5.47 P. 11.16 S 2.16 N Theory 5.49 P. 11.32 S 2.48 N Timken O.K. load 45 lbs.
EXAMPLE 2 Analysis 3.63 N. 3.98 P 8.1 '71 S Theory 3.58 70 N. 3.97 "/1 P 8.18 7r S Timken O.K. load 60 lbs.
EXAMPLE 3 Di-isobutyl dithiophosphoric acid (250g. 1m) was added to toluene di-isocyanate (174g. 1m) from a tap funnel over a period of /4 hour at 7080C. After being left for 2 hours, with stirring, 2-ethylhexanol (143g. 1.1m) was added dropwise over a period of 1 hour. After a further /2 hour, stirring and heating was stopped, the product was filtered and stripped to 120C. and 4 torr to yield 525 g. (96.3%).
Analysis: 5.67 I P 4.95 N. 11.12 S. Theory 5.67 P. 5.14 N. 11.72 7r S. Timken O.K. load 45 lbs.
EXAMPLE 4 Isobutanol (14.8g., 0.2m) was added dropwise over hour to toluene di-isocyanate (34.8g., 0.2m.), initially at 7080C., causing the temperature to rise briefly to l 10C. 0,0-di-tridecyl dithiophosphoric acid (110.2g., 0.2m) was then added, dropwise over one hour, with the temperature being maintained at 7080C. A further quantity of isobutanol (1.5g, 10%) was then added to ensure that there was no free isocyanate in the product, and the mixture stirred for acid one hour to yield 157g. (97.5%) of a greenish yellow liquid containing 3.97%P (theory 4.18).
Timken O.K. load 50 lbs.
EXAMPLE a. Toluene di-isocyanate 174g, 1.0m) was heated to approximately 105C. and 0,0-di-isobutyl dithiophosphoric acid (250g. 1.0m) run in over /4 hour and left to react for a further 2 /4 hours at 105C.
b. To 100g. (0.24m.) of the product of (a) was added n-dodecyl mercaptan (47.5g., 0.24m) over 20 minutes at approximately 105C. After stirring for a further /2 hour the product was cooled to yield 146g. (99%) of an olive green liquid containing 5.0%P and 16.4%S (theory 5.02% and 15.55% respectively).
EXAMPLE 6 3,5,5-Trimethyl hexanol (57.6g., 0.4m) was added to toluene di-isocyanate (69.6g., 0.4m.) at a temperature of 70-80C. and 0,0'-di-isobutyl dithiophosphoric 106g, 0.4m.) was added to the reaction product dropwise over a one hour period, followed by reaction for a further 1 A hours. A yield of 223g. (95.5%) ofa dark grey/green semi-solid containing 5.85%P (theory 5.52%) was obtained.
Timken O.K. load 27 lbs.
EXAMPLE 7 Toluene di-isocyanate (69.6g., 0.4m.) was added to tridecanol (80.0g., 0.4m.) at 7080C., and to the reaction product was added 0,0'-di-isobutyl dithiophosphoric acid (l06.8g., 0.4m.) dropwise over hour. The reaction was continued with stirring for a further hour to yield 245g. (99%) of a green, slightly viscous liquid containing 5.44%P (theory 5.04%).
Timken O.K. load 30 lbs.
EXAMPLE 8 Tridecanol (40.0g., 0.2m.) was added to toluene diisocyanate (34.8g.. 0.2m.) over /2 hour at a temperature of 7080C. and the product stirred for a further V2 hour. To the product was then added 0,0'-di-isobutyl dithiophosphoric acid (55.6g., 0.2m.) over /4 hour followed by a further 4.0g. (10%) of tridecanol and the reaction continued for a further one hour to yield 1 19g. (95% of an olive green liquid containing 5.00%? (theory 5.04%
Timken O.K. load 45 lbs.
EXAMPLE 9 An 0,0-dialkyl dithiophosphoric acid was prepared by reaction of P 5 with Alfol 20-22 (a commercially available mixture of alcohols containing 20-22 carbon atoms). To toluene di-isocyanate (34.8g., 0.2m.) was added, in bulk. 2-ethylhexanol (26g, 0.2m.), causing an exotherm. To the product was added the 0,0'-di- Alfol 20-22 dithiophosphoric acid (150g.,0.2m.), after melting. causing the temperature to rise to 50C. The total addition time of the dithiophosphoric acid was hour. after which the reaction was continued for a further 1 /2 hours to yield 205g. (97.5%) of a grey/green solid containing 2.77%P (theory 2.93%).
Timken O.K. load 60 lbs.
EXAMPLE 10 a. lsobutanol (74.0g., 1.0m.) was added dropwise to toluene di-isocyanate 174g, 1.0m.) over 1: hour, during which time the initial temperature of 30C. rose to C. due to the strong exotherm. The reaction was continued, with stirring, for a further one hour.
b. To the reaction product of (a) (7l.0g., 0.5m.) was added 0,0'-di-tridecyl dithiophosphoric acid (276g, 0.5m.) over A hour, an exotherm being noticed. The reaction temperature was 35C. The final product was a light green liquid containing 4.72%P and 9.7%S (theory 4.18% and 8.62% respectively) and was obtained in a yield of 333g. (96%).
Timken 0.K. load 45 lbs.
EXAMPLE 1 1 To the reaction product (7l.0g., 0.5m.) of Example 10(a) was added 0,0'-di-nonylphenyl dithiophosphoric acid (260g, 0.5m.) at 30C. over 34 hour. The reaction was continued for a further one hour at 35C. to yield 320g. (96.5%) of a yellow viscous liquid containing 4.44%P and 9.6%S (theory 3.96% and 8.18% respectively).
Timken O.K. load 60 lbs.
EXAMPLE 12 EXAMPLE l3 lsobutanol l4.8g., 0.2m.) was added in bulk to toluene di-isocyanate (69.6g., 0.4m.) and reacted for one hour at 30-45C. 0,0-di-2-ethylhexyl dithiophosphoric acid (76.8g., 0.2m.) was added dropwise over 1 hour at 30C. and reaction contined for /2 hour. To 129g. of the resulting product was added. at 25C., mole equivalents of isobutanol (12.3g.) and 0,0'-di-2- ethylhexyl dithiophosphoric acid (63.6g.) over a period of hour. After reacting for 1 /2 hours at 25C. there was obtained 201 g. of a mobile, light green liquid containing 4.75%P (theory 5.15%).
EXAMPLE l4 Toluene di-isocyanate (69.6g., 04m.) and 2- ethylhexanol (26.0g., 0.2m.) were reacted for 1 hour at about 3045C. 0,0'-di-2-ethylhexyl dithiophosphoric acid (76.8g., 0.2m.) was then added dropwise over hour at 30C. and reaction continued for 1 hour. To 156g. of the resulting product were added mole equivalents of 0,0'-di-2-ethylhexyl dithiophosphoric acid (67.9g.) and 2-ethylhexamol (22.4g.) and reaction continued, with stirring, for 2 hours at a temperature of 20C. There was obtained 235g, (95.4%) of a green liquid containing 4.15%P (theory 4.71%).
Timken O.K. load 35 lbs.
EXAMPLE l5 Toluene di-isocyanate (69.6g., 0.4m.) and isobutanol (29.6g., 0.4m.) were reacted for 2 hours, the temperature exotherming to 75c. at one stage. There was then added, at 30C. over 4 hour, 132.8g. (0.4m.) of an 0,0'-dia1kyl dithiophosphoric acid prepared from P S and. Alfol 6 (commercially available mixture of alcohols having about 6 carbon atoms). Reaction was continued, with stirring, for a further one hour to yield 215g. (92.6%) of an olive green liquid containing 5.93%? (theory 5.68%).
EXAMPLE 16 Toluene di-isocyanate (69.6g., 0.4m.) and tridecanol (800g, 0.4m.) were reacted together and 0,0'-di-Alfol 6 dithiophosphoric acid 132.6g., 0.4m.) added over hour, with the temperature at 3035C. The reaction was continued for a further 1 hour to yield 270g. (96%) of a light green liquid containing 4.49%P (theory 4.61%).
Timken O.K. load 50 lbs.
EXAMPLE 17 The procedure of Example 16 was repeated using toluene di-isocyanate (69.6g., 0.4m.) and Alfol 6 (40.8g., 0.4m.) (with a strong exotherm to 80C.), and 0,0-ditridecyl dithiophosphoric acid (216g, 0.4m.) to yield 32 l g. (98.5%) ofa light green viscous liquid containing 3.95%P (theory 4.03%).
Timken 0.14.. load 40 lbs.
EXAMPLE 18 The procedure of Example 16 was repeated using toluene (ii-isocyanate (69.6g., 0.4m.), 2-ethylhexanol (520g, 0.4m.), and 0,0-di-tridecyl dithiophosphoric acid (216g, 0.4m.) to yield 327g. (98%) ofa very light green mobile liquid containing 3.74%? (theory 3.89%).
Timken O.K. load 50 lbs.
EXAMPLE 19 The procedure of Example 16 was repeated using toluene di-isocyanate (696g, 0.4m.) 3,5,5- trimethylhexanol (57.6g., 0.4m.), and 0,0-di-isobutyl dithiophosphoric acid (106.8g., 0.4m.) to yield 21 lg. (90.5%) of a light green solid containing 5.63%? (theory 5.22%).
Timken O.K. load 40 lbs.
EXAMPLE 20 isodecanol (79g, 0.5m.) was added to toluene diisocyanate (87g, 0.5m.) over A hour. The initial temperature was 50C., exotherming strongly to a maximum 105C. The reaction mixture was cooled to 80C. and stirred for a further 1 1 hour. 0,0'-di-isobutyl dithiophosphoric acid 134g., 0.5m.) was then added over A hour, keeping the temperature at 7580C., and the mixture stirred for a further 14 hour, whereafter isodecanol (7.9g, was added to ensure completion of reaction. There was obtained 201g. (96%) of a light green fairly mobile liquid containing 5.3%P (theory 5.4%).
Timken O.K. load 40 lbs.
EXAMPLE 21 In a manner identical to Example 20, except that a dry nitrogen stream was passed through the reaction mixture to prevent moisture absorption by toluene diisocyanate, there was prepared from toluene diisocyanate (435g, 2.5m.), isodecanol (395g, 2.5m.)
10 and 0,0'-di-isobutyl dithiophosphoric acid (670g, 2.5m.) a clear, light green liquid containing 5.45%! and 12.0%S (theory 5.4% and 1 1.15% respectively).
EXAMPLE 22 This was a repetition of Example 21, identical in every respect, and the product contained 5.3%P and 12.0%S.
Timken O.K. load 40 lbs.
EXAMPLE 23 An 0,0'-di-P1B phenyl dithiophosphoric acid was prepared from P S and a polyisobutenyl substituted phe-' EXAMPLE 24 Phenyl isocyanate (23.8g., 0.2m.) was weighed carefully into a flask and 0,0'-di-isobutyl dithiophosphoric acid (52.6g., 0.2m.) slowly added thereto. The resulting reaction was vigorously exothermic, causing a maximum temperature of 90C. to be obtained. Stirring was continued for hour and the final product was a dark green liquid.
EXAMPLE 25 Toluene di-isocyanate (17.4g., 0.1m.) was placed in a flask and 0,0'-di-isobutyl dithiophosphoric acid (268g, 0.1m.) added thereto. The reaction mixture was stirred at -80C. for 1 /2 hours and then tridecanol (20g, 0.1m.) added thereto and stirred for a further hour. The final product was a very viscous, almost colourless liquid containing 5.3%P (theory 5.3%).
EXAMPLES 26 TO 31 Further examples were carried out in asimilar manner to Example 1, the relevant details of these further examples being set out in Table 1 hereinafter.
The products of various of the foregoing Examples 1 to 31 were tested for suitability as lubricant additives, as also were five prior art additives in accordance with US. Pat. No. 3,537,998. The prior art additives were prepared as follows:
Additive l. [Toluene-2,4-dis-(S-carbamoyl-0,0'-di-2- hexadecyl dithiophosphate Toluene di-isocyanate (17.4g., 0.1m.) was placed in a flask and 0,0'-di-hexadecyl dithiophosphoric acid (127g, 0.2m.) added thereto, the acid being added warm from a beaker due to its waxy nature when cold. The addition of the dithiophosphoric acid produced an exotherm. After completion of the addition the reaction mixture was heated to 70-80C. for 2 /2 hours, to yield a cloudy, quite viscous liquid containing 4.63%P
(theory 4.66%). The product solidified after standing overnight.
Additive 2. [To1uene-2,4-di-(S-carbamoyl-0,0'-ditridecyl dithiophosphate Toluene di-isocyanate (7.81 g., 0.066m.) was added dropwise to 0,0-di-tridecy1 dithiophosphoric acid (44.5g., 0.09m.) at 7080C., an exotherm being noticed after each addition. Reaction was continued for I la hours at 70-80C. to yield a very pale green liquid containing 5.35%? and 10.3%S (theory 5.34% and 11.03% respectively).
Additive 3. [To1uene-2.4-di-(S-carbamoyl-0,0'-di-pnonylphenyl dithiophosphate)] 0,0-di-p-nonylphenyl dithiophosphoric acid (54.5g., 0.1m.) was added in small increments to a well-stirred solution of toluene di-isocyanate (8.71g., 0.05m.) in benzene (65ml. The rate of addition was such that the resulting exotherm did not raise the reaction temperature above 25C., the temperature being maintained below 25C. throughout. After completion of the addition the product was vacuum stripped to remove the solvent and the final product was a light green viscous liquid containing 5.10%P and 10.16%S (theory 5.05% and 9.39% respectively).
Additive 4. [Toluene-2,4-di-(S-carbamoyl-0,0'-di-2- ethylhexyl dithiophosphate)] This was prepared in a similar manner to Additive 3, from 0,0'-di-2-ethylhexyl dithiophosphoric acid (50.0g. 0.133m.) and a solution of toluene diisocyanate l l.45g., 0.066m.) in benzene (25ml) The resulting additive was a mobile. green liquid containing 6.72%P and 4.48%S (theory 7.03% and 14.35% respectively).
Additive 5. [Toluene-2,4-di-(S-carbamoyl-0,0'-dioctylphenyl dithiophosphate)] This additive was also prepared in a similar manner to Additive 3, from 0,0-di-octylphenyl dithiophosphoric acid (202.4g., 0.4m.) and a solution of toluene di-isocyanate (34.8g., 0.2m.) in benzene (80ml). The resulting additive was a viscous, light green liquid containing 4.70%? and 10.58%S (theory 5.23% and 10.80% respectively).
In order to evaluate the antiwear (load-carrying) properties of the additives of the present invention the products of a number of the preparations exemplified above were tested by means of the Timken O.K. load test in accordance with the Institute of Petroleums Test Method IP/240/69. The apparatus employed comprises a roller mounted on a spindle, the roller being rotated against a seated metal block lubricated with the test blend. Also mounted on the spindle is a lever system to one end of which is applied a weight, the weight being increased until the test blend fails as judged by scoring of the seated metal block. The blends tested consisted of sufficient of the test additives to provide a phosphorus content of 0.072% by weight in a base oil which was 150 Solvent Neutral mineral oil having viscosities of about 33 and 5 cSt at 100F. and 210F. re spectively. The base oil alone had a Timken O.K. load of 12 lbs. and the results obtained with the various test additives are as set out above in each relevant example. Typical results obtained in this test with the widely used zinc 0.0-di-hydrocarbyl dithiophosphates, at 0.08% by weight phosphorus level, are 33 lbs. (hydrocarbyl mixed isobutyl and pentyl groups), 35 lbs. (hydrocarbyl mixed isopropyl and capryl groups) and 12 lbs. (hyerties various blends were tested by means of the R0- tary Bomb test carried out at 150C. and in the presence of water in the manner described in the left-hand column of page 220 of the article entitled Evaluation of Antioxidants for Automotive Lubricants Using the Rotary Bomb" in the Journal of the Institute of Petroleum Vol. 55, No. 544, July 1969, Pages 219 to 226. The blends tested consisted of a base oil and sufficient of the products of the examples to provide a phosphorous content of 0.072% by weight, the results obtained being as follows:
Time to Induction Break Base Oil only 45 min. Base oil product of Example 1. 122 min. Base oil product of Example 2. 78 min. Base oil product of Example 3. 402 min. Base oil product of Example 26. 129 min. Base oil product of Example 27. 88 min.@ Base oil Additive 4. 405 min. Base oil Additive 2. 298 min. Base oil Additive 3. 82 min.@ Base oil Additive 5. 124 min.
500 Solvent Neutral mineral oil having viscositics of about 1 l0 and 11 C51. at 100F. and 210F. respectively. em 25 p.s.i. loss.
Engine tests and tests on a Cam and Tappet machine to simulate in service performance of blends containing the additives of the present invention were also carried out. The engine tests indicated that the additives of the present invention were comparable in efficiency with the widely used zinc 0,0'-di-hydrocarbyl dithiophosphates and good results were obtained on the Cam and Tappet machine.
To test Thermal Stability (deposit forming tendencies) blends of base oil (same as in Timken O.K. load tests) containing sufficient of various additives to provide a phosphorus content of 0.5% by weight, were placed in pyrex test tubes (ml. of test blend in each). The test tubes were then suspended for 1 hour in an oil bath maintained at a temperature of 175 180C. so that about 1 inch of the blend was showing above the surface of the oil bath.
Meanwhile, sintered glass crucibles had been cleaned, flushed through with acetone, dried in an oven at 100C. for about /2 hour, cooled in air and weighed.
After completion of the 1 hour immersion period, each blend was poured into approximately 200ml. of heptane and the resulting mixture filtered as quickly as possible through a crucible. The crucible contents were then thoroughly rinsed with clean heptane to ensure all oil was removed, then dried in the oven for about /2 hour, cooled in air and re-weighed. The results obtained were expressed as the weight of precipitate collected/weight of additive in blend X 100% In this way were evaluated blends containing one of the aforesaid prior art additives and blends containing the product of Example 25, the results being as follows:
, Blends containing prior art additive 3.92%
droclrbyl g y 'p y P Blends containing Product of Example 25 0.65%
For a qualitative demonstration of antioxidant propmean value ofduplicalc was.
TABEE i EX. Dithiophosphoric Reaction Product Additional %P in Product %S in Product NO. lsocyanate Acid Temp. Notes (C.) Found Theory Found Theory Ethyl di-p-nonylphenyl olive green lsocyanate added over 26 27.6g. 206g. -s0 liquid /4 hour 5.14 5.12 10.3 10.58
TAB LE l Continued EX. Dithiophosphoric Reaction Product Additional %P in Product 7rS in Product NO. lsocyanate Acid Temp. Notes (C.) Found Theory Found Theory (0.4m.) (0.4m.) H 3- w W WW4 W t-Butyl di-tridccyl grey/green lsocyanate added over 27 297g. l54.8g. 80-85 liquid 1% hour and product 5.l7 523 I079 l0.80
(0.3m.) (0.3m.) reacted at 70C. for
further one hour. t-Butyl di-p-nonylphenyl yellow lsocyanate added over 28 297g. l54.5g. 70-80 liquid /z hour and product 5.09 4.82 8.89 9.95
(0.3m) (0.3m.) reacted at 70C. for
further one hour. t-Octadi-tridecyl lsocyanate added over 29 decyl 2l3g. -40 i hour and reaction 3.70 3.93
ll8g. (0.4m.) continued for further (0.4m.) 1% hours with temp.
gradually returning to 20C. t-Octadi-tsobutyl lsocyanate added over decyl 107g. 20-35 hour and reaction 5.66 5.78
l ltlg. (0.4m.) continued for further (0.4m) one hour. Small solid particles noticed and filtered off, but further precipitate formed subsequently and whole product eventually solidified. Allyl di-isodecyl 20-45 mobile Acid added dropwise to 3| 8.3 47g. yellow liquid isocyanate at room (0.lm.) (0.lm.) temperature resulting in 6.52 6.2 13.9 l2.9
exotherrn to 45C Stirred for 2% hours We claim: 6. A composition according to claim 1 containing 1. A lubricant composition consisting essentially of lubricating oil having dissolved therein from about 0.1 to 10% by weight of at least one oil-soluble dithiophosphoric acid derivative having the general formula:
wherein R is selected from the group consisting of mono-valent aliphatic groups, mono-valent aromatic groups. di-valent aliphatic groups and di-valent aromatic groups; X is selected from the group consisting of oxygen atoms and sulphur atoms; R is an alkyl group; R and R are the same or different and are selected from the group consisting of alkyl groups, alkaryl groups, aryl groups, aralkyl groups and alkenyl groups; and n is 0 when R is a mono-valent group and n is I when R is a divalent group.
2. A composition according to claim 1 wherein R and R are selected from the group consisting of alkyl, alkaryl and aralkyl groups containing from 4 to 18 carbon atoms.
3. A composition according to claim 1 wherein R is an alkyl group containing from 4 to 13 carbon atoms.
4. A composition according to claim 1 wherein R is selected from the group consisting of a mono-valent alkyl group containing from I to 18 carbon atoms and a divalent aryl group.
5. A composition according to claim 4 wherein R is a divalent aryl group bearing at least one alkyl substitutent and containing from 6 to 24 carbon atoms.
wherein R is selected from the group consisting of mono-valent aliphatic groups, mono-valent aromatic groups, di-valent aliphatic groups and di-valent aromatic groups; X is selected from the group consisting of oxygen atoms and sulphur atoms; R is an alkyl group; R and R are the same or different and are selected from the group consisting of alkyl groups, alkaryl groups, aryl groups, aralkyl groups and alkenyl groups; and n is 0 when R is a mono-valent group and n is 1 when R is a di-valent group.

Claims (8)

1. A LUBRICANT COMPOSITION CONSISTING ESSENTIALLY OF LUBRICATING OIL HAVING DISSOLVED THEREIN FROM ABOUT 0.1 TO 10% BY WEIGHT OF AT LEAST ONE OIL-SOLUBLE DITHIOPHOSPHORIC ACID DERIVATIVE HAVING THE GENERAL FORMULA:
2. A composition according to claim 1 wherein R1 and R2 are selected from the group consisting of alkyl, alkaryl and aralkyl groups containing from 4 to 18 carbon atoms.
3. A composition according to claim 1 wherein R4 is an alkyl group containing from 4 to 13 carbon atoms.
4. A composition according to claim 1 wherein R3 is selected from the group consisting of a mono-valent alkyl group containing from 1 to 18 carbon atoms and a divalent aryl group.
5. A composition according to claim 4 wherein R3 is a divalent aryl group bearing at least one alkyl substitutent and containing from 6 to 24 carbon atoms.
6. A composition according to claim 1 containing from 0.5 to 5% by weight of the dithiophosphoric acid derivatives.
7. A composition according to claim 1 containing in addition to the dithiophosphoric acid derivatives, from about 0.1 to 5% of a compound selected from the group consisting of mono-octyl phenyl-Alpha -naphthylamines, mono-octyl phenyl- Beta -naphthylamines, mono-nonyl phenyl- Alpha -naphthylamines and mono-nonyl phenyl-Beta -naphthylamines.
8. An oil concentrate or additive package comprising from 10% to 70% by weight of a lubricating oil having dissolved therein from 90% to 30% by weight of at least one dithiophosphoric acid derivative having the formula:
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US5405545A (en) * 1993-03-02 1995-04-11 Mobil Oil Corporation Antiwear and antioxidant additives
US6001783A (en) * 1997-03-24 1999-12-14 The Lubrizol Corporation Mixed polysulfides and lubricants and functional fluids containing the same
WO2007131891A1 (en) * 2006-05-15 2007-11-22 Shell Internationale Research Maatschappij B.V. Lubricating oil composition
US20080051307A1 (en) * 2004-07-27 2008-02-28 The Lubrizol Corporation Lubricating Compositions Containing An Ester Of A Polycarboxylic Acylating Agent

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US2743235A (en) * 1952-06-27 1956-04-24 Exxon Research Engineering Co Mineral oil composition
US3317425A (en) * 1963-10-15 1967-05-02 Shell Oil Co Lubricating compositions containing a carbamoyl phosphine
US3446738A (en) * 1964-02-10 1969-05-27 Sinclair Research Inc Ester base lubricant compositions containing an aromatic amine and an organic thiophosphite or thiophosphonate
US3537998A (en) * 1968-06-17 1970-11-03 Chevron Res Bis thiophosphoro carbamyl lubricating oil antioxidants

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Publication number Priority date Publication date Assignee Title
US2648696A (en) * 1951-06-19 1953-08-11 Shell Dev Mixed acid anhydrides and process for production of same
US2743235A (en) * 1952-06-27 1956-04-24 Exxon Research Engineering Co Mineral oil composition
US3317425A (en) * 1963-10-15 1967-05-02 Shell Oil Co Lubricating compositions containing a carbamoyl phosphine
US3446738A (en) * 1964-02-10 1969-05-27 Sinclair Research Inc Ester base lubricant compositions containing an aromatic amine and an organic thiophosphite or thiophosphonate
US3537998A (en) * 1968-06-17 1970-11-03 Chevron Res Bis thiophosphoro carbamyl lubricating oil antioxidants

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5405545A (en) * 1993-03-02 1995-04-11 Mobil Oil Corporation Antiwear and antioxidant additives
US6001783A (en) * 1997-03-24 1999-12-14 The Lubrizol Corporation Mixed polysulfides and lubricants and functional fluids containing the same
US20080051307A1 (en) * 2004-07-27 2008-02-28 The Lubrizol Corporation Lubricating Compositions Containing An Ester Of A Polycarboxylic Acylating Agent
WO2007131891A1 (en) * 2006-05-15 2007-11-22 Shell Internationale Research Maatschappij B.V. Lubricating oil composition
US20090186789A1 (en) * 2006-05-15 2009-07-23 Mitsuhiro Nagakari Lubricating oil composition

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