Classifications

• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
  • C10M135/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing sulfur, selenium or tellurium
  • C10M135/02—Sulfurised compounds
  • C10M135/04—Hydrocarbons
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  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
  • C10M135/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing sulfur, selenium or tellurium
  • C10M135/32—Heterocyclic sulfur, selenium or tellurium compounds
  • C10M135/34—Heterocyclic sulfur, selenium or tellurium compounds the ring containing sulfur and carbon only
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  • 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
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  • 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
  • C10M2215/22—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
  • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
  • C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
  • C10M2219/02—Sulfur-containing compounds obtained by sulfurisation with sulfur or sulfur-containing compounds
  • C10M2219/022—Sulfur-containing compounds obtained by sulfurisation with sulfur or sulfur-containing compounds of hydrocarbons, e.g. olefines
• • 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
  • C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
  • C10M2219/10—Heterocyclic compounds containing sulfur, selenium or tellurium compounds in the ring
• • 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
  • C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
  • C10M2219/10—Heterocyclic compounds containing sulfur, selenium or tellurium compounds in the ring
  • C10M2219/102—Heterocyclic compounds containing sulfur, selenium or tellurium compounds in the ring containing sulfur and carbon only in the ring
• • 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
  • C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
  • C10M2219/10—Heterocyclic compounds containing sulfur, selenium or tellurium compounds in the ring
  • C10M2219/104—Heterocyclic compounds containing sulfur, selenium or tellurium compounds in the ring containing sulfur and carbon with nitrogen or oxygen in the ring
• • 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
  • C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
  • C10M2219/10—Heterocyclic compounds containing sulfur, selenium or tellurium compounds in the ring
  • C10M2219/104—Heterocyclic compounds containing sulfur, selenium or tellurium compounds in the ring containing sulfur and carbon with nitrogen or oxygen in the ring
  • C10M2219/106—Thiadiazoles
• • 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
  • C10M2223/00—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
  • C10M2223/02—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having no phosphorus-to-carbon bonds
  • C10M2223/04—Phosphate esters
• • 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
  • C10M2223/00—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
  • C10M2223/02—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having no phosphorus-to-carbon bonds
  • C10M2223/04—Phosphate esters
  • C10M2223/042—Metal salts thereof
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
  • C10N2040/00—Specified use or application for which the lubricating composition is intended
  • C10N2040/02—Bearings
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
  • C10N2070/00—Specific manufacturing methods for lubricant compositions
  • C10N2070/02—Concentrating of additives

Definitions

• ABSTRACT A process for preparing an oil-soluble metal-free phosphorus-free substance for use as a lubricating additive, which comprises sulphurising a compound having the general formula:
• Lubricating compositions may contain a major amount of lubricating oil and a minor amount of the said sulphurised compound. preferably, the said sulphurised compound is incorporated into the lubri eating composition in an amount of from 0.1 to 10% by weight.
• This invention relates to sulphurised products having utility as lubricant additives and lubricating composi tions containing them.
• the invention also relates to a process for preparing sulphurised products, the products so prepared and lubricating compositions containing such products.
• sulphurised products which are, at least in the preferred embodiments, very effective antioxidants in lubricating compositions such as crankcase lubricants.
• the sulphurised products are also useful for other purposes, for example as loadcarriers in gear oil formulations.
• a lubricating composition containing a major amount of lubricating oil and a minor amount of a sulphur containing additive wherein said additive is a sulphur containing norbornenyl compound having the general formula:
• each of R, R and R when taken singly is a hydrogen atom, an alkyl group containing from 1 to about 15 carbon atoms, an aryl group containing from 6 to about 15 carbon atoms or a cycloalkyl group containing from 4 to about 10 carbon atoms;
• each of R and R when taken singly is a hydrogen atom, an alkyl group containing from 1 to about 15 carbon atoms; an aryl group containing from 6 to about 15 carbon atoms; a cycloalkyl group containing from 4 to about 10 carbon atoms or an alkenyl group containing from 2 to about 10 carbon atoms or R and R taken together form the group CHY.
• CY CY in which Y is a hydrogen atom or a methyl group or R together with R form an alkylidene group containing from 1 to about 6 carbon atoms; and
• R is a hydrogen atom or an alkyl group containing from 1 to about 15 carbon atoms; or, wherein said additive is the oil-soluble sulphur containing norbornenyl product resulting from sulphurising a compound having the general formula:
• R, R, R R, R and R are as hereinbefore defined at a temperature of up to C, said sulphurisation being carried out in the absence of a solvent or in the presence of a non-polar solvent.
• R. R. R R, R, and R are as hereinbeforc defined. at a temperature of up to lBU C, said sulphurisation being carried out in the absence of a solvent or in the presence of a non-polar sovent, and thereafter removing any oil-insoluble constituents from the resulting sulphurised product.
• Examples of compounds which maybe sulphurised in the process of the present invention are norbornene. S-vinylnorborncnc. dicyclopentadienc and methyl cyclopentadiene dimer of which dicyclopcntadienc and methyi cyclopentadienc dimer are especially preferred.
• the process of the present invention may he carried out in the presence of a catalyst of the type commonly used in sulphurisation reactions, for example tertiary amines such as triethylarninc or pyridine, secondary amines such as di'isopropylamine, di butylamine. and dicyclohexylaminc and primary amines such as cyclohexylamine and the 'yo-dirnethyl tertiary alkyl primary amines available commercially under such trade names as Primcne JM T and Prirncne Sl-R.
• a catalyst of the type commonly used in sulphurisation reactions for example tertiary amines such as triethylarninc or pyridine, secondary amines such as di'isopropylamine, di butylamine. and dicyclohexylaminc and primary amines such as cyclohexylamine and the 'yo-dirnethyl
• the amount of catalyst used is not critical, but normally will be about t).l to 109'? for example, from 2 to more preferably [ll to 10% and most preferably 0.3 to 2%. by weight based on the weight of the compound to be sulphurised.
• the process of the present invention may also be carried out in the presence of a small amount, cg. not more than molar percent based on the compound to be sulphurised, of a solubilising agent.
• solubilising agents which may be used are:
• Conjugated dior poly-olefins such as alloocimcne l,5 dirnethyll.4,h-octatriencl
• Non-coniugated dior poly olefins such as cyclododecatrienc and lfi-cyclooctadicne Dialkyl maleates, preferably containing from 1 to 12,
• each alkyl group cg. dibutyl maleatc Alkenyl succinic acids or anhyriridcs thereof. preferably containing 8 to II carbon atoms in the alkenyl group.
• Polyisobutenyl succinimides Mercaptobenzothiarole Bcnr'othiazole disulphide
• Alkenoic acids preferably containing from h to IR carbon atoms such as olcic acid
• Alkyl esters of alkenoic acids such as octyl methacrylate
• Ethoxylated amines such as the material available commercially under the trade name Ethomeen Tl 5 (ill 4 Dimcrised alkenoic acids, preferably containing from 18 to 36 carbon atoms Dicyclopentadiene hydrate Alkanols, such as isodecanol.
• solubilising agents may assist in increasing the proportion of oil-soluble constituents in the product of the sulphurisation reaction and, when used, will normally be present in an amount of l to 25, preferably 2 to l5, molar percent. Within this range it is preferred to use as small an amount of solubilising agent as possible consistent with obtaining a reasonable amount of oil-soluble product (for example not more than 25-30filby weight, preferably less, of the product should be oil-insoluble).
• the effectiveness of the solubilising agent has been found to be dependent in part on the proportion of sulphur used in the sulphurisation reaction. effectiveness decreasing with increasing proportions of sulphur used.
• solubilising agents are more ef fective than others and solubilising agents such as alloocimcne, dibutyl maleatc, dodecenyl succinic acid, t-dodeeyl mercaptan, Ethomeen Tli, olcic acid and mercaptobenrruhiazole are most preferred.
• the sulphur is preferably used in an amount of from 0.1 to 4 moles per mole of compound to be sulphurised, with an amount of about 1 to 2 moles per mole of compound to be sulphurised being most preferred.
• the sulphurisation can be conveniently carried out by merely mixing the reactants, including any catalyst. and/or solubilising agent used, and heating.
• the compound to be sulphurised can be added to hot sulphur.
• reaction temperature of at least C. is preferred, with at least 0 or l()OC. being most preferred for providing the preferred sulphurised materials as hereinbefore described.
• a reaction temperature no greater than l6tlC is preferred.
• Sulphurisation is normally completed in from 0.5 to 24 hours depend ing on the reaction temperature. At the optimum temperature of about llll to l4UC. a reaction time of about 2 hours is generally found to be most satisfac' tory, the co-rcactants either being mixed and heated for 1 hours or the sulphur being added to the com pound to be sulphurised in portions over, for example l hour at l2UC and this temperature then being maintained for a further hour,
• the sulphurisation may, if desired, be carried out in an inert atmosphere such as a nitrogen blanket.
• the pressure at which the sulphurisation is carried out is not critical, but is preferably not reduced to a level at which significant amounts of the compound being sulphurised are lost from the reaction system by distillation.
• a non-polar solvent examples of the latter being petroleum ether, toluene, benzene, xylene and mineral oil (especially a mineral lubricating oil).
• any oilinsoluble constituent of the product may be removed by any convenient method using well known techniques such as solvent extraction or dissolving in oil followed by filtration. However, if the reaction is carried out under careful control at the optimum conditions the whole product is frequently oil-soluble and removal of oil-insoluble constituents is not necessary. Accordingly, reference made herein and in the appended claims to removal of oil-insoluble constituents is to be understood to mean. unless the context denotes otherwise, removal of oil-insoluble constituents if, and as,
• a preferred technique for removal of oil-insoluble by products is to initially strip off excess olefin which would otherwise solubilize the insoluble component and to then add excess petroleum ether to precipitate an insoluble phase which can be removed. The petro leurn ether is then stripped off to yield a totally oilsoluble product.
• dicyclopentadiene is sulphurised using 2 moles of sulphur per mole of dicyclopentadiene at a temperature of about l20C using di-isopropylamine and 2,5- bis(t-octyldithio)-l,3,4- thiadiazole as catalysts, and, optionally, one of the most preferred solubilisers listed above.
• the present invention also includes the oil-soluble, metal-free, phosphorus-free products prepared by the process of the present invention.
• the sulphurised olefins of the present in vention may contain, as a result of contaminants present in the starting materials, a trace of metal and/or phosphorus.
• traces should be present in such minute quantities as to be of no practical significance and it is to be understood that the starting materials should not be grossly contaminated with metal and/or phosphorus compounds.
• commercially available grades of starting materials are normally completely adequate in this respect and any contamination arising therefrom is far below any level of practical significance.
• the products of the process of the present invention preferably contain from about to 40% by weight of sulphur and reaction conditions and proportions of coreactants may be adjusted in order to vary the sulphur content of the product. Further the products of the process of the present invention are believed to contain substantial amounts of the trithiolan derivatives hereinbefore depicted in formula (A).
• the lubricating compositions of the present invention comprise from 0. l% to l0%, more preferably 0.25% to 5%, by weight of the oil-soluble, metalfree, phosphorus-free products and/or compounds of foregoing formula (A) and the lubricating oil may be any of the well known mineral or synthetic oils of appropriate viscosity characteristics.
• the lubricating compositions of the present invention may also contain, if desired, conventional lubricant additives such as ancillary antioxidants and anti-wear additives (preferably ashless), corrosion inhibitors, dispersants, particularly dispersants of the succinimide type, detergents, thickeners, pour-point depressants and viscosity index improvers.
• a particularly useful additive to be used in conjunction with the additives of the present invention is benzotriazole which has been found to reduce lacquer formation and improve the appearance of bearings in test engines lubricated with compositions of the present invention.
• the benzotriazole may, if desired. be incorporated prior to the sulphurisation reaction of the present invention or after sulphurisation but either before or after the removal of any oil-insoluble constituents.
• the additives of the present invention may also be conveniently prepared as a concentrate consisting of a concentrated solution of a major amount of the additives and a minor amount of mineral oil, or as an additive package consisting of a concentrated solution in mineral oil of a major amount of a combination of the additives with one or more conventional additives.
• Such concentrates and packages are frequently very convenient forms in which to handle and transport additives and are diluted with further quantities of oil, and optionally blended with further additives. before use.
• a solution comprising a major amount of one or more compounds having the formula (A) or one or more of the oil-soluble metal free. phosphorus-free products of the process of the invention and a minor amount of a lubricating oil.
• One or more conventional additives may be combined with the compounds of formula (A) or the oil soluble. metal-free, phosphorus-free products.
• EXAMPLE 1 A mixture of dicyclopentadiene (264g.m 20m) and triethylamine catalyst (132g) was added dropwise over a period of 1 hour to sulphur (128g, 4.0m) maintained at a temperature of about C. About half-way through this addition an exotherm to C. was n0 ticed and this was quickly controlled by air blast cooling and no further problems were encountered during the remainder of the addition. After completion of the addition the resulting reaction mixture was maintained at l40l45C. for a further 1 hour, whereafter about 0.2g hydroquinone was added to the resulting crude product.
• the crude product was stripped under high vacuum (0.2mm. Hg) to a base temperature of C. (internal temperature 140C.) to yield 330g (84% by weight) of a distillate (predominantly unrcacted dicyclopentadiene).
• the residue was placed in a l litre separating funnel together with an amount of petroleum ether (B.Pt. 6268C.) sufficient to substantially fill the funnel resulting in a viscous, oily, petroleum etherinsoluble layer (yield 2l2.lg., 541% by weight) and a petroleum ether layer.
• the latter was separated and the petroleum ether stripped off to yield 149.2g. (38.2% by weight) of the final. oil-soluble product containing 32.5% sulphur.
• EXAMPLE 4 Dicyclopentadiene (238g, 1.8m) sulphur (64g, 2.0m), triethylamine catalyst 14.2g.) and, as solubilising agent, dibutyl maleate (45.6g 0.2m) were mixed and heated to l40150C. for 2 hours. Hydroquinone (about 0.2g) was added to the crude product which was then stripped to 120C. at 0.2mm Hg. to yield 83g. (23.9% by weight) distillate. The residue was worked up in the same manner as in Example 1 to yield about lg. insoluble material and 250.3g (72.0% by weight) oil-soluble product containing 24.7% sulphur.
• EXAMPLE 15 A mixture of dicyclopentadiene 178g, 1.35m) dibutyl maleate (34.2g., 0.15m.) and triethylamine 10.6g.) was heated to 140C. and sulphur (72g, 2.25m) was added thereto over a period of 50 minutes during which the temperature was maintained at 140C. The temperature was maintained at 140C. for a further 70 minutes whereafter 0.2g. hydroquinone was added and the crude product stripped to 150C. 140C. internal temperature) at 0.1mm Hg. to yield 57g. (20.1% by weight) distillate. The residue was worked up in the same manner as in Example 1 to yield 32.6g.(11.5% by weight) insoluble material and 184.3g. (64.8% by weight) oil-soluble product containing 28.4% sulphur.
• Example 31 was repeated except in that the reaction temperature was kept at 90C. and extraction with petroleum ether was not carried out to yield 184g. (50.4%) excess cyclopentadiene, no insoluble material and 386g. (68.0%) soluble product containing 35.5%8.
• Example 32 was repeated, except in that the reaction temperature was kept at 120C., to yield 120g excess cyclopentadiene, no insoluble material and 455g. soluble product containing 31.9%S.
• EXAMPLE 43 Sulphur (172.8g., 5.4m.) was added incrementally over 1% hours, at a temperature of C., to a mixture of dicyclopentadiene (356g., 2.7m.), dibutyl maleate (68.4g., 0.3m.) diisopropylamine (5g.) and sodium sulphide powder (5g.). The reaction mixture was then stirred for a further 2 hours with the reaction temperature maintained in the range of 8590C. The resulting product was then filtered and stripped to 120C. under water pump vacuum to yield 83g. distillate (excess dicyclopentadiene). The stripped product (462g.) was not fully oil soluble and was therefore boiled with 1% litres petroleum ether to yield 350g. (59%) of soluble product containing 33.8%5.
• Example 44 was repeated using 500 ml petroleum ether (boiling point 80-100C.) in place of the toluene.
• the reaction temperature was maintained in the range of 100l10C. throughout due to the volatility of the solvent. In this way was obtained 469.9g. (78.2%) of soluble product containing 36.2%S.
• EXAMPLE 46 Dicyclopentadiene (178g. 1.35m), dibutyl maleate (34.2g., 0.15m), di-isopropylamine (2g.) and 2,5-bis (octyldithio) -l,3,4-thiadiazole (2g) were dissolved in 200g. of high viscosity index 100 Solvent Neutral mineral oil. Sulphur (86.4g., 2.7m) was added incrementally over 1 hour at -l20C. and the reaction temperature maintained at C. for a further 1 hour. The product was vacuum stripped and filtered to yield 461g. (92.4%) of oil soluble product containing 19.0%S.
• EXAMPLE 48 Example 44 was repeated except in that 172.8g. (5.4m) sulphur was used and a reaction temperature of 110C. was used. There was obtained 19] .4g. (49.9%) soluble product and 138.6g (36.1%) insoluble product.
• EXAMPLE 49 S-Vinylnorbornene (84g. 0.7m), diisopropylamine (4.0g) and 2,5-bis (t-octyldithio) -l ,3,4-thiadiazole (0.8g) were mixed, heated to 130C. and sulphur (22.4g.. 0.7m) added thereto portionwise over 1 hour. The temperature was maintained at l30C. for a further 1 hour and the reaction mixture was stripped to 100C. at 0.1mm Hg. to remove 20.8g. (l9.6%) unreacted 5-vinylnorbornene. The product was extracted with 250ml petroleum ether (boiling point 6268C.) and filtered to remove a small quantity of insoluble material. The petroleum ether was stripped from the extract to yield 51g (48%) of soluble product.
• Load carrying properties were determined using the Timken OK load test according to the lP240/69T method (except in that results are quoted in lbs.)
• the test blends consisted of test additive dissolved in l50 Solvent Neutral mineral oil, the former being in amount to provide 0.3% by weight sulphur in the test blend and the results were as follows:
• Timken OK Load (lbs) In comparison commercially available zinc dialkyl dithiophosphates usually give Timken OK loads of 35-40 lbs in this test.
• Petter Wl Engine tests were carried out by the lnstitute of Petroleums method lP 176/69 using an ashless blend consisting of a commercially available suc- Test Additive Induction Period (minutes) cinimide-type dispersant. a secondary aromatic amine N bas l I antioxidant and a combination of corrosion inhibitors gg f g z 3 together with 1.0% by weight of the test additive all disdo. l] 178 solved in a 500 Solvent Neutral mineral oil. Bearing 33' iggus i l .S. S weight losses after a 36 hour test were measured and do, I9 216 25 gm. 13:5) were as follows: 3 I12 (25 p.s.i.
• interengaging surfaces lubricated with the test blend and are driven at speeds in a ratio of 14.6:1. After a short running period the load on the interengaging surface is incrementally increased until 5 scuffing occurs.
• the additives of the present invention impart antioxidant properties (Rotary Bomb Test) and yet have a low level of corrosiveness (Copper Strip Test) despite the high sulphur content. Furthermore in the standard tests the additives demonstrate load carrying abilities (Timken OK load Test) and test engine performance (Peter WI Tests) in fully formulated blends similar to those exhibited by the zinc dialkyl dithiophosphates normally used in premium grade crankcase lubricants.
• EXAMPLES 16 in 30 'Elhnmeen T 15 is a Commercially mail-able ctlhuxylatcd lilllfi amine of average molecular weight 482 and Containing an average of S ethylene oxide residues per mulccule. "Methylc clupcnlzidicnc dimer used in place of dicyclnpentadienc.
• Example 42 (Columns (1 to 8) inclusive Example [20C at US 32.3 ll.l 426 70.4 34.5
• each of R, R and R when taken singly is selected from the group consisting of a hydrogen atom. an alkyl group containing from 1 to about 15 carbon atoms, an aryl group containing from 6 to about 15 carbon atoms and a cycloalkyl group containing from 4 to about carbon atoms;
• each of R and R when taken singly is selected from the group consisting of a hydrogen atom, an alkyl group containing from 1 to about carbon atoms, an aryl group containing from 6 to about 15 carbon atoms, a cycloalkyl group containing from 4 to about 10 carbon atoms and an alkenyl group containing from 2 to about 10 carbon atoms;
• R is selected from the group consisting of a hydrogen atom and an alkyl group containing from I to about 15 carbon atoms; and (2) an oil-soluble sulphurised norbornenyl product resulting from sulphurising a compound having the general formula:
• R, R, R R, R and R are as hereinbefore defined at a temperature of up to lC.. said sulphurisation being carried out in the absence of a solvent or in the presence of a non-polar solvent.
• a lubricating composition according to claim 2 which comprises from 0.1 to l0 by weight of the additive.
• a lubricating composition according to claim 1 which incorporates a minor amount of benzotriazole therein.
• a lubricating composition according to claim 6 which comprises from 0.1 to 10% by weight of the additive.
• a lubricating composition according to claim 8 which comprises from 0.25 to 5 percent by weight of the additive.
• a lubricating composition according to claim 6 wherein said sulphurized norbornyl product is that resulting from sulphurizing a compound having the formula (B) with from about I to 2 moles of sulphur per mole of compound.
• a solubilizing agent selected from the group consisting of alloocimene, dibutyl maleate, dodecenyl succinic acid, t-dodecyl mercaptan, ethoxylated tallow amine having an average molecular weight of 482 and containing an average of 5 ethylene oxideresidues per molecule, oleic
• a concentrate for addition to a lubricating composition comprising a minor amount of a mineral oil and a major amount of a sulphurcontaining additive selected from the group consisting of (l) sulphurised norbornenyl compound having the general formula:
• each of R, R and R when taken singly is selected from the group consisting of a hydrogen atom, an
• alkyl group containing from 1 to about 15 carbon atoms, an aryl group containing from 6 to about 15 carbon atoms and a cycloalkyl group containing from 4 to about 10 carbon atoms;
• each of R and R when taken singly is selected from the group consisting of a hydrogen atom, an alkyl group containing from 1 to about [5 carbon atoms, an aryl group containing from 6 to about 15 carbon atoms, a cycloalkyl group containing from 4 to about 10 carbon atoms and an alkenyl group containing from 2 to about 10 carbon atoms;
• R is selected from the group consisting of a hydrogen atom and an alkyl group containing from 1 to about 15 carbon atoms; and (2) an oil-soluble sulphurised norbornenyl product resulting from sulphurising a compound having the general formula:
• R, R R R R and R are as hereinbefore defined at a temperature of up to C, said sulphurisation being carried out in the absence of a solvent or in the presence of a non-polar solvent.

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• Chemical & Material Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• General Chemical & Material Sciences (AREA)
• Oil, Petroleum & Natural Gas (AREA)
• Organic Chemistry (AREA)
• Lubricants (AREA)
• Nitrogen- Or Sulfur-Containing Heterocyclic Ring Compounds With Rings Of Six Or More Members (AREA)

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• 0
  • NL NL159136D patent/NL159136C/xx active
• 1973
  • 1973-04-12 GB GB1772873A patent/GB1470649A/en not_active Expired
• 1974
  • 1974-01-01 AR AR253275A patent/AR208174A1/es active
  • 1974-04-10 JP JP4160874A patent/JPS5347124B2/ja not_active Expired
  • 1974-04-10 BR BR2912/74A patent/BR7402912D0/pt unknown
  • 1974-04-11 AT AT304674A patent/AT341537B/de not_active IP Right Cessation
  • 1974-04-11 DE DE2417864A patent/DE2417864C3/de not_active Expired
  • 1974-04-11 IT IT21301/74A patent/IT1007869B/it active
  • 1974-04-11 BE BE143102A patent/BE813603A/xx not_active IP Right Cessation
  • 1974-04-11 US US459938A patent/US3882031A/en not_active Expired - Lifetime
  • 1974-04-11 FR FR7412738A patent/FR2225431B1/fr not_active Expired
  • 1974-04-11 CA CA197,455A patent/CA1047476A/en not_active Expired
  • 1974-04-11 ZA ZA00742357A patent/ZA742357B/xx unknown
  • 1974-04-11 NL NL7405010.A patent/NL159136B/xx not_active IP Right Cessation
• 1977
  • 1977-01-12 JP JP281377A patent/JPS52107009A/ja active Granted
  • 1977-10-05 SE SE7711154A patent/SE7711154L/xx unknown

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