US2734863A - Properties of guanidine salt of pjst-treated - Google Patents

Properties of guanidine salt of pjst-treated Download PDF

Info

Publication number
US2734863A
US2734863A US2734863DA US2734863A US 2734863 A US2734863 A US 2734863A US 2734863D A US2734863D A US 2734863DA US 2734863 A US2734863 A US 2734863A
Authority
US
United States
Prior art keywords
product
iron
treated
phospho
hydrocarbon
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
Publication date
Application granted granted Critical
Publication of US2734863A publication Critical patent/US2734863A/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Classifications

    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M137/00Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing phosphorus
    • C10M137/16Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing phosphorus having a phosphorus-to-nitrogen bond
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2203/00Organic non-macromolecular hydrocarbon compounds and hydrocarbon fractions as ingredients in lubricant compositions
    • C10M2203/10Petroleum or coal fractions, e.g. tars, solvents, bitumen
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2223/00Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
    • C10M2223/12Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions obtained by phosphorisation of organic compounds, e.g. with PxSy, PxSyHal or PxOy
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2225/00Organic macromolecular compounds containing phosphorus as ingredients in lubricant compositions
    • C10M2225/04Organic macromolecular compounds containing phosphorus as ingredients in lubricant compositions obtained by phosphorisation of macromolecualr compounds not containing phosphorus in the monomers
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10NINDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00Specified use or application for which the lubricating composition is intended
    • C10N2040/04Oil-bath; Gear-boxes; Automatic transmissions; Traction drives
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10NINDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00Specified use or application for which the lubricating composition is intended
    • C10N2040/04Oil-bath; Gear-boxes; Automatic transmissions; Traction drives
    • C10N2040/042Oil-bath; Gear-boxes; Automatic transmissions; Traction drives for automatic transmissions
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10NINDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00Specified use or application for which the lubricating composition is intended
    • C10N2040/04Oil-bath; Gear-boxes; Automatic transmissions; Traction drives
    • C10N2040/044Oil-bath; Gear-boxes; Automatic transmissions; Traction drives for manual transmissions
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10NINDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00Specified use or application for which the lubricating composition is intended
    • C10N2040/04Oil-bath; Gear-boxes; Automatic transmissions; Traction drives
    • C10N2040/046Oil-bath; Gear-boxes; Automatic transmissions; Traction drives for traction drives
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10NINDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00Specified use or application for which the lubricating composition is intended
    • C10N2040/08Hydraulic fluids, e.g. brake-fluids
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10NINDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00Specified use or application for which the lubricating composition is intended
    • C10N2040/135Steam engines or turbines
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10NINDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00Specified use or application for which the lubricating composition is intended
    • C10N2040/14Electric or magnetic purposes
    • C10N2040/16Dielectric; Insulating oil or insulators
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10NINDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00Specified use or application for which the lubricating composition is intended
    • C10N2040/14Electric or magnetic purposes
    • C10N2040/17Electric or magnetic purposes for electric contacts
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10NINDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00Specified use or application for which the lubricating composition is intended
    • C10N2040/20Metal working
    • C10N2040/22Metal working with essential removal of material, e.g. cutting, grinding or drilling
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10NINDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2050/00Form in which the lubricant is applied to the material being lubricated
    • C10N2050/10Semi-solids; greasy
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10NINDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2070/00Specific manufacturing methods for lubricant compositions
    • C10N2070/02Concentrating of additives

Definitions

  • the results are unexpected since it has been conventional in the art to employ glassor enamel-lined equipment or other ceramic-type reaction zones for the preparation of phospho-sulfurized hydrocarbons in order to avoid degradation of the product. It now has been found that treatment in the presence of these metals improves rather than degrades the material. Treatment with iron is particularly beneficial and is preferred in the present invention.
  • treatment with at least one of the metals heretofore mentioned is carried out during at least one stage of the preparation of the phospho-sulfurized hydrocarbon or the guanidino and reactive olefinic derivatives thereof.
  • the treatment is conducted at an elevated temperature for a suificient time and with adequate contact with the metal surface, to form a stable, non-corrosive material that is substantially free of iron and copper.
  • the treatment is carried out at a temperature above about 300 F., preferably above 400 F. As "a rule, it is preferred that the temperature not exceed about 500 to 600 F. since degradation of the product may occur at higher temperatures.
  • the treatment will be carried out for a time sufficient to stabilize the material, the time depending upon the type of material being treated as well as the extent of metal surface present and the temperature. A time in the range of about /2 to 10 hours will generally be sufiicient.
  • the amount of iron or copper or mixtures thereof employed during the treatment may be varied considerably. It is preferred that at least a portion of the metal be in finely divided form, such as powder, shavings, pellets, shot, steel wool and the like.
  • the finely divided metal may be added to the material with stirring and the stirring continued during at least part of the treating period in order to insure good contact. In such cases,
  • the solid material is separated from the phospho-sulfurized material by filtration, such as through a diatomaceous earth or the like, or by other means.
  • the treatment may also be carried out in a reactor or treating vessel constructed of iron or copper or in a reactor that is lined with one of these metals.
  • efiicient stirring or agitating devices be employed in order to obtain contact of the metal surface by the material being treated.
  • the metal surface should be free of oxide or sulfide films or the like which generally render the metal inactive for performing the desired stabilizing function.
  • Metal-lined treating zones may be activated by washing with a dilute mineral acid, polishing, or the like before use, Water washing if necessary to remove excess acid and drying.
  • the iron may be in the form of pure iron, cast iron, mild steel, steel alloys including small amounts of other alloying metals, and the like.
  • Treatment in a metal lined container is generally less preferable than treatment with a finely divided metal; in the former case it is difficult to control the extent of contact with a metal surface and deactivating films frequently formed thereon. In addition longer treating times are usually required in the case of the metal-lined reactors.
  • a preferred procedure is to carry out the reaction or treatment in a zone lined with the desired metal and employ at the same time a smaller amount of finely divided metal than would be used in the case where the treatment is carried out in a glassor enamel-lined reaction zone.
  • the metal treating step may occur at one or more stages of the preparation of the phospho-sulfurized hydrocarbon or its derivatives.
  • the phosphosulfurization may be carried out at the conventional conditions of temperature and time of contact in the presence of metal as heretofore described, followed by filtration if necessary.
  • the presence of the metal does not affect adversely the phospho-sulfurization step nor does the metal form a salt or other organo-metallic constituent that remains in the finished products.
  • the phospho-sulfurization step may be conducted by conventional procedures following which the finished product is after-treated with the metallic material.
  • the phospho-sulfurized hydrocarbon prepared by either of the above procedures may be used as such or may be further treated with guanidino or reactive olefinic compounds by procedures to be described hereinafter to produce superior ashless detergents.
  • the phosphosulfurized hydrocarbon produced by conventional procedures is reacted with guanidino or reactive olefinic.
  • the compounds in the presence of iron or copper or the guanidino and reactive olefinic derivatives may be aftertreated with these metals. While the preparation should include at least one treatment with the metal, it may be desired to contact the material with the metal during two or more stages of the preparation. For example, the phospho-sulfurization step may be carried out in an iron reactor, the guanidino derivative formed, and the resulting product treated with powdered iron or copper. It will be obvious to one skilled in the art that other modifications and combinations may be employed.
  • the phospho-sulfurized hydrocarbon used in the present invention is one prepared by procedures well known to the art. Conveniently it is prepared by reaction of a substantially non-olefinic hydrocarbon material with a reactive sulfurand phosphorus-containing material which is defined herein as being a sulfide of phosphorus, which may be P283, P255, P483, and P457, or mixtures of the elements sulfur and phosphorus or other such reactive materials. Preferably, phosphorus pentasulfide, P285, is used.
  • the phospho-sulfurization is generally carried out at a temperature of about 200 F. to about 600 F., and preferably from about 300 F.
  • reaction is preferably carried out in a non-oxidizing atmosphere, such as an atmosphere of nitrogen. It is usually desirable to use an amount of a phosphorusand sulfurcontaining material that willgive a product having at least about 1.0 weight of both sulfur and phosphorus in chemically combined form.
  • the reaction time is generally not critical, the time required being that to cause a practically maximum proportion of the reactive sulfur and phosphorus-containing material to react under the temperature conditions employed. -A reaction time from 2 to hours is generally necessary. The time should be adequate for substantially complete reaction. it desired, the reaction product may be further treated by blowing 'with steam, alcohol, ammonia, or the like at an elevated temperature in the range of about 200 F. to improve the odor thereof, but this further treatment is generally unnecessary since metal treatment substantially accomplishes such improvements.
  • non-olefinic hydrocarbon materials may be reacted with the phosphorus sulfide.
  • Such hydrocarbons include paraflins, aromatics, cyclo-aliphatics, petroleum fractions, such as lubricating oil distillates, pet-rolatums,waxes, or condensation products of petroleum fractions, solvent extracts of petroleum fractions, and the like.
  • Aromatic hydrocarbons such as'benzene, naphthalene, anthracene, Xylenes, and those having alkyl substituents and aliphatic hydrocarbons having aryl substituents may be employed.
  • Condensation products of halogenated aliphatic hydrocarbons with an aromatic compound produced by condensation in the presence of a Friedel-Crafts type catalyst may be used.
  • Particularly desirable, and preferred in the practice of the present invention are essentially non-olefinic lubricant base stocks such as bright stock residuums and'the like.
  • Substantially non-olefinic hydrocarbons that have been phosphosulfurized do not react with the 'metal treating agent in such manner as to form organo-metallic materials or other ash-forming constituents that remain in the finished product. It is desirable to avoid these.
  • the guanidino derivatives of the phospho-sulfurized hydrocarbon are prepared by neutralizing the titratable acidity of the above phospho-sulfurized reaction product (metal-treated or untreated) with guanidine or a-derivative thereof.
  • the free base guanidine and its derivatives may be used as well as basic acting salts of such bases, by which is meant salts of acids whose strength, measured on a pH scale, is less than the acidic phosphorus-sulfide hydrocarbon product.
  • Such basic acting salts include the carbonates of guanidine and its derivatives.
  • the products may be formed if desired by doubledecomposition of a salt of guanidine or guanidine derivative, such as guanidine hydrochloride or sulfate, with a metal salt of the phospho-sulfurized hydrocarbon reaction product.
  • a salt of guanidine or guanidine derivative such as guanidine hydrochloride or sulfate
  • metal salt of the phospho-sulfurized hydrocarbon reaction product may be formed if desired by doubledecomposition of a salt of guanidine or guanidine derivative, such as guanidine hydrochloride or sulfate, with a metal salt of the phospho-sulfurized hydrocarbon reaction product.
  • guanidine and its salts are preferred, substituted guanidines may be used.
  • guanidino compounds used in the practice of the present invention may be defined by the formula in which R, R, and R" represent hydrogen or hydrocarbon groups containing 1 to carbon atoms, e. g, straight chain alkyl groups, such as methyl, ethyl, propyl, butyl and also higher straight and branched chain alkyl groups, such as octyl, isooctyl, 2-ethylhexyl, decyl, dodecyl, tetradecyl, cetyl and stearyl radicals.
  • R, R, and R" represent hydrogen or hydrocarbon groups containing 1 to carbon atoms, e. g, straight chain alkyl groups, such as methyl, ethyl, propyl, butyl and also higher straight and branched chain alkyl groups, such as octyl, isooctyl, 2-ethylhexyl, decyl, dodecyl,
  • R, R and R" may also represent cycloalkyl, arylalkyl, aryl or alkylaryl groups, as previously mentioned, for'example, methylcyclohexylQphenylethyl, phenyl, cresyl, and tort-butylphenyl groups. It will be understood that R, R and R can be the same or diiferent atoms or groups in the same molecule. However, in the case of a substituted guanidine it is most preferable to employ symmetrically tri-substituted compounds, and alkyl and cycloalkyl groups are the more preferred types of substituting groups.
  • substituted guanidines include the monoalkyl, mononaphthenyl, and monoaralkyl guanidines; unsymmetrical dialkyl dinaphthenyl, and diarylalkyl guanidines.
  • Somewhat less preferable but still useful classes are the symmetrical dialkyl, dinaphthenyl, and diarylalkyl guanidines, and the mono-, di-, and triaryl guanidines.
  • Still other substituted guanidines may be used, such as biguanide, dicyandiamide, and dicyandiamidine.
  • guanidine In addition to guanidine, the following specific guanidino derivatives may be used:
  • Thesubstantially neutralized phospho-sulfurized hydrocarbon product is prepared by reaction with a basic guanidino-compound of the above type, preferably in a non-oxidizing atmosphere, by contacting the latter with the phospho-sulfurized material as such or dissolved in a suitable solvent such as naphtha at a temperature of about 100 F. to 400 F. It is generally desired to employ at least enough of the basic compound to neutralize the titratable acidity of the phospho-sulfurized hydrocarbon product. Inpractice a somewhat greater amount of basic compound is generally used since the basic compound can be reacted in proportions greater than that required for neutralization of titratable acidity.
  • a water-soluble basic compound such as 'guanidine carbonate may be dissolved in water and then contacted with the phospho-sulfurized hydrocarbon. Metal treatment may then be carried out if desired.
  • the metal-treated or untreated phospho-sulfurized hydrocarbon may instead be reacted with an unsaturated hydrocarbon to form the olefinic derivative by contacting the two materials at room temperature. More preferably a somewhat elevated temperature of the order of 380 F. is used with from about 0.1% to 50%, preferably about 5% to 20%, by weight of the unsaturated hydrocarbon, based on the amount of phospho-sulfurizcd hydrocarbon present.
  • the reaction is continued for a period of about one to about ten hours.
  • the unreacted olefin is removed from the final product by distillation.
  • This last step may also be made more effective by the addition of an agent commonly used in the vulcanization of rubber, such as Tuads, Captax, Tellurac, or Selenac.
  • After-treatment with iron or copper may then be conducted, usually at a temperature'above that used in forming the olefinic derivative.
  • the unsaturated hydrocarbon material which is reacted with the phospho-sulfurized hydrocarbon in accordance with the present invention may be any aliphatic, cycloaliphatic, terpenic, or aliphatic-aromatic hydrocarbon containing at least one olefinic double bond carbon-to-carbon linkage in a non-aromatic group.
  • the materials more preferably employed include the o'lefins, ,e.
  • the additives of the present invention are to be dissolved in mineral oils, the hydrocarbons which are reacted with sulfurand phosphorus-containing material and the materials which are further reacted with the products thus formed will be chosen with a view to provide a product which .is soluble in the oil base or which has such marginal solubility that it can be plasticized with a high molecular weight alcohol, esters, or other plasticizer.
  • additives of the present invention When additives of the present invention are employed in mineral lubricating oils, they are preferably added in proportions of about 0.001 to about 20% and preferably 1.0% to about 12.0%. The proportions giving the best results will vary somewhat according to the nature of the additive and the specific purpose which the lubricant is to serve in agiven case. For commercial purposes, it is convenient to prepare concentrated oil solutions in which the amount of additive in the composition ranges from about 20% to 50% or higher by weight, and to transport and store them in such form. In preparing a lubricating oil composition for use as a crankcase lubricant, the additive concentrate is merely blended with the base oil in the required amount.
  • Example l Preparation of P255 treated bright stocks
  • Pass-treated bright stock a solvent extracted, dewaxed, deasphalted bright stock from Mid-Continent crude
  • the product was considerably more stable, as regards both the tendency to form oil-insoluble precipitates and the tendency to evolve H28, than products obtained from the same reaction in enamel or glass reactors. This is shown by the data in the table below. It should be noted that the phosphorus contents of the products prepared in glass and iron were essentially identical but the sulfur content of the material prepared in iron was significantly lower.
  • PROPERTIES OF Pass-TREATED BRIGHT STOCKS Reactor Material Product Analysis E I name or 11011 lass Phosphorus, wt. percent a 1. 8-2.0. Sulfur, wt. percent.” 3. 7-4. 7.
  • the method as modified comprising immersing a polished metallic copper strip in the oil to be tested for a period of three hours at 210 F. and noting the extent of the staining. Ratings are given on a scale of from 1 to 10 which denotes discoloration ranging from no stain to a black surface film.
  • Example Ill-Preparation of guanidine salt of P285- treated bright stock totally in iron In the example above only the P285 treatment was carried out in an iron reactor. In the present-example, the total reaction including the neutralization was carried out in iron. 1000 .grarnsof a solvent extracted Mid-Continent bright stock of approximately 150 :Saybolt seconds viscosity at 210 F. was charged to :an ordinary black iron (cast iron) pot sitting on a hot plate. . The bright stock was stirred and also blown with N2 and the temperature raised to 300 F. in one-half hour. At that point 300 grams of P285 were added and the temperature was raised to 450 F. The product was soaked at 450 F. for five hours and then filtered using Hy-flo filter aid while hot.
  • the Pass-bright stock'prepared in A above was also converted to the guanidine salt, however no iron treatment was used.
  • 130 pounds of the bright stock was treated with 13 pounds of 'guanidine carbonate 8 in 1.0 pounds of water and the addition was made at 135 F.
  • the reaction mixture was heated to 320 F; over an eight hour period and held at 320 F. for two hours before filtering.
  • Example VI Treatment of P2S5-treated bright stock with copper .
  • the diisobutylene-PzSs-bright stock reaction product was then treated with (by weight) of finely divided metallic iron at 400 F. for three hours, after which it was filtered. These materials were evaluated for hydrogen sulfide stability, and for copper and silver corrosivity as 2.5 wt. percent blends in an' SAE-30 grade solvent extracted Mid-Continent lubricating oil base stock containing 2.5 wt. percent of an oil concentrate of a calcium petroleum sulfonate.
  • Example VIII .Aviati0n C. F. R. engine evaluation A sample of Pass-treated bright stock prepared in an iron reactor (Example I) was evaluated at 6.0 wt. percent in a 120 grade aviation oil in an aviation C. F. R. engine test. The results of this test show that the blend gave considerably less deposits than the base stock as illustrated in the data in the table below. The test consisted of 50 hours of operation at 1800 R. P. M. and 4 brake horsepower. The oils were rated on a demerit system where a perfectly clean surface is given a rating of zero and 10 is equivalent to the worst condition that could be expected.
  • the products of the present invention are particularly useful as ashless detergents in aviation engine lubricating oils and the like. They may be employed in ordinary hydrocarbon lubricating oils, in heavy duty type of lubricants along with other additives of the conventional types, and with various synthetic lubricants such as those prepared by polymerization of olefins, by the reaction of oxides of carbon with hydrogen, or by other means.
  • the conventional synthetic oils of the ester, polyester and polyether types may also be used alone or in combination with mineral lubricants as base oils.
  • the lubricating oils may .vary considerably in viscosity and other properties, de-
  • additives of the present invention may be used along with the additives of the present invention in compounding the lubricants.
  • the additives of the present invention may also be used in motor fuels, hydraulic fluids, cutting oils, turbine oils,
  • a process as in claim 1 wherein said contacting with said metal is carried out at a temperature above about 300 F.
  • a hydrocarbon oil composition containing a detergent quantity of a product selected from the class consisting of a phospho-sulfurized substantially non-olefinic hydrocarbon materials and the guanidino and reactive olefinic derivatives thereof, said materials containing at least 1.0 weight per cent of both phosphorus and sulfur in chemically combined form; which product has been contacted during at least one stage of the preparation thereof with a metal selected from the class consisting of iron and copper at elevated temperatures and for an extended period of time, adequate to produce a substantially odorless, non-corrosive product.
  • a composition as in claim 12 in which said nongreases olefinic hydrocarbon is .a lubricating oil base stock.
  • vA composition as in claim 12 wherein said guanidino-derivative is prepared by treatment with guanidine carbonate.
  • composition as in claim 12in which said phospho-sulfurized hydrocarbon is prepared by treatment with Pass.
  • composition as in claim 12 which includes from about 0.001 to 20 weight per cent of said product.
  • a concentrate comprising essentially a lubricating oil and above about'20% of the product of claim .8.
  • the improvement which comprises contacting at least a portion of said reaction 12 product during at least one stage of said process with a metal selected from the class consisting of iron and copper at a temperature in the range of about 300 to 500 F., whereby a substantially stable and non-corrosive product is "formed.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Chemistry (AREA)
  • Lubricants (AREA)

Description

PHOSPHO-SULFURIZED HYDROCARBONS Robert H. Jones, Irvington, N. Y., and Max W. Hill Somerville, and Leonard E. Moody, Cranford, N. J. assignors to Esso Research and Engineering Company, a corporation of Delaware No Drawing. Application November 1, H51, Serial No. 254,442
21 Claims. (Cl. 25232.7)
nited States Patent deposits or ash. Such additives, however, are not completely stable under storage conditions, sometimes have poor odor, and in other cases are corrosive to bearing metals and other engine parts under operating conditions.
It is the principal object of the present invention to disclose a novel method for treating the phosphosulfurized materials with iron or copper under conditions such that improvements are obtained in the additive and in oils containing the additive. The results are unexpected since it has been conventional in the art to employ glassor enamel-lined equipment or other ceramic-type reaction zones for the preparation of phospho-sulfurized hydrocarbons in order to avoid degradation of the product. It now has been found that treatment in the presence of these metals improves rather than degrades the material. Treatment with iron is particularly beneficial and is preferred in the present invention.
In accordance with the present invention, treatment with at least one of the metals heretofore mentioned is carried out during at least one stage of the preparation of the phospho-sulfurized hydrocarbon or the guanidino and reactive olefinic derivatives thereof. The treatment is conducted at an elevated temperature for a suificient time and with adequate contact with the metal surface, to form a stable, non-corrosive material that is substantially free of iron and copper.
The treatment is carried out at a temperature above about 300 F., preferably above 400 F. As "a rule, it is preferred that the temperature not exceed about 500 to 600 F. since degradation of the product may occur at higher temperatures. The treatment will be carried out for a time sufficient to stabilize the material, the time depending upon the type of material being treated as well as the extent of metal surface present and the temperature. A time in the range of about /2 to 10 hours will generally be sufiicient.
The amount of iron or copper or mixtures thereof employed during the treatment may be varied considerably. It is preferred that at least a portion of the metal be in finely divided form, such as powder, shavings, pellets, shot, steel wool and the like. The finely divided metal may be added to the material with stirring and the stirring continued during at least part of the treating period in order to insure good contact. In such cases,
in the range of about 0.5 to 50% by weight, preferably a about 2 to by weight, based on the material being treated will be adequate for stabilization purposes. After the treating or soaking period has been completed, the solid material is separated from the phospho-sulfurized material by filtration, such as through a diatomaceous earth or the like, or by other means.
The treatment may also be carried out in a reactor or treating vessel constructed of iron or copper or in a reactor that is lined with one of these metals. In this case, it is essential that efiicient stirring or agitating devices be employed in order to obtain contact of the metal surface by the material being treated. The metal surface should be free of oxide or sulfide films or the like which generally render the metal inactive for performing the desired stabilizing function. Metal-lined treating zones may be activated by washing with a dilute mineral acid, polishing, or the like before use, Water washing if necessary to remove excess acid and drying. The iron may be in the form of pure iron, cast iron, mild steel, steel alloys including small amounts of other alloying metals, and the like.
Treatment in a metal lined container is generally less preferable than treatment with a finely divided metal; in the former case it is difficult to control the extent of contact with a metal surface and deactivating films frequently formed thereon. In addition longer treating times are usually required in the case of the metal-lined reactors. A preferred procedure is to carry out the reaction or treatment in a zone lined with the desired metal and employ at the same time a smaller amount of finely divided metal than would be used in the case where the treatment is carried out in a glassor enamel-lined reaction zone.
The metal treating step may occur at one or more stages of the preparation of the phospho-sulfurized hydrocarbon or its derivatives. For example, the phosphosulfurization may be carried out at the conventional conditions of temperature and time of contact in the presence of metal as heretofore described, followed by filtration if necessary. The presence of the metal does not affect adversely the phospho-sulfurization step nor does the metal form a salt or other organo-metallic constituent that remains in the finished products. If desired, the phospho-sulfurization step may be conducted by conventional procedures following which the finished product is after-treated with the metallic material. The phospho-sulfurized hydrocarbon prepared by either of the above procedures may be used as such or may be further treated with guanidino or reactive olefinic compounds by procedures to be described hereinafter to produce superior ashless detergents.
In other and preferred modifications, the phosphosulfurized hydrocarbon produced by conventional procedures is reacted with guanidino or reactive olefinic.
compounds in the presence of iron or copper or the guanidino and reactive olefinic derivatives may be aftertreated with these metals. While the preparation should include at least one treatment with the metal, it may be desired to contact the material with the metal during two or more stages of the preparation. For example, the phospho-sulfurization step may be carried out in an iron reactor, the guanidino derivative formed, and the resulting product treated with powdered iron or copper. It will be obvious to one skilled in the art that other modifications and combinations may be employed.
The phospho-sulfurized hydrocarbon used in the present invention is one prepared by procedures well known to the art. Conveniently it is prepared by reaction of a substantially non-olefinic hydrocarbon material with a reactive sulfurand phosphorus-containing material which is defined herein as being a sulfide of phosphorus, which may be P283, P255, P483, and P457, or mixtures of the elements sulfur and phosphorus or other such reactive materials. Preferably, phosphorus pentasulfide, P285, is used. The phospho-sulfurization is generally carried out at a temperature of about 200 F. to about 600 F., and preferably from about 300 F. to about 550 F., using from about '1 to about 10, preferably about 2 to about 5, molecular proportion of the sulfide of phosphorus. The reaction is preferably carried out in a non-oxidizing atmosphere, such as an atmosphere of nitrogen. It is usually desirable to use an amount of a phosphorusand sulfurcontaining material that willgive a product having at least about 1.0 weight of both sulfur and phosphorus in chemically combined form. The reaction time is generally not critical, the time required being that to cause a practically maximum proportion of the reactive sulfur and phosphorus-containing material to react under the temperature conditions employed. -A reaction time from 2 to hours is generally necessary. The time should be adequate for substantially complete reaction. it desired, the reaction product may be further treated by blowing 'with steam, alcohol, ammonia, or the like at an elevated temperature in the range of about 200 F. to improve the odor thereof, but this further treatment is generally unnecessary since metal treatment substantially accomplishes such improvements.
A wide variety of non-olefinic hydrocarbon materials may be reacted with the phosphorus sulfide. Such hydrocarbons include paraflins, aromatics, cyclo-aliphatics, petroleum fractions, such as lubricating oil distillates, pet-rolatums,waxes, or condensation products of petroleum fractions, solvent extracts of petroleum fractions, and the like. Aromatic hydrocarbonssuch as'benzene, naphthalene, anthracene, Xylenes, and those having alkyl substituents and aliphatic hydrocarbons having aryl substituents may be employed. Condensation products of halogenated aliphatic hydrocarbons with an aromatic compound produced by condensation in the presence of a Friedel-Crafts type catalyst may be used. Particularly desirable, and preferred in the practice of the present invention, are essentially non-olefinic lubricant base stocks such as bright stock residuums and'the like. Substantially non-olefinic hydrocarbons that have been phosphosulfurized do not react with the 'metal treating agent in such manner as to form organo-metallic materials or other ash-forming constituents that remain in the finished product. It is desirable to avoid these.
The guanidino derivatives of the phospho-sulfurized hydrocarbon are prepared by neutralizing the titratable acidity of the above phospho-sulfurized reaction product (metal-treated or untreated) with guanidine or a-derivative thereof. The free base guanidine and its derivatives may be used as well as basic acting salts of such bases, by which is meant salts of acids whose strength, measured on a pH scale, is less than the acidic phosphorus-sulfide hydrocarbon product. Such basic acting salts include the carbonates of guanidine and its derivatives. The products may be formed if desired by doubledecomposition of a salt of guanidine or guanidine derivative, such as guanidine hydrochloride or sulfate, with a metal salt of the phospho-sulfurized hydrocarbon reaction product. Although guanidine and its salts are preferred, substituted guanidines may be used.
Broadly, guanidino compounds used in the practice of the present invention may be defined by the formula in which R, R, and R" represent hydrogen or hydrocarbon groups containing 1 to carbon atoms, e. g, straight chain alkyl groups, such as methyl, ethyl, propyl, butyl and also higher straight and branched chain alkyl groups, such as octyl, isooctyl, 2-ethylhexyl, decyl, dodecyl, tetradecyl, cetyl and stearyl radicals. R, R and R" may also represent cycloalkyl, arylalkyl, aryl or alkylaryl groups, as previously mentioned, for'example, methylcyclohexylQphenylethyl, phenyl, cresyl, and tort-butylphenyl groups. It will be understood that R, R and R can be the same or diiferent atoms or groups in the same molecule. However, in the case of a substituted guanidine it is most preferable to employ symmetrically tri-substituted compounds, and alkyl and cycloalkyl groups are the more preferred types of substituting groups. These include the symmetrical trialkyl, trinaphthenyl, and triarylalkyl guanidines. Also highly preferred classes of substituted guanidines include the monoalkyl, mononaphthenyl, and monoaralkyl guanidines; unsymmetrical dialkyl dinaphthenyl, and diarylalkyl guanidines. Somewhat less preferable but still useful classes are the symmetrical dialkyl, dinaphthenyl, and diarylalkyl guanidines, and the mono-, di-, and triaryl guanidines. Still other substituted guanidines may be used, such as biguanide, dicyandiamide, and dicyandiamidine.
In addition to guanidine, the following specific guanidino derivatives may be used:
a-Methylguanidine a-Decylguanidine a,a-Diisoamylguanidine a,ot-Dicyclohexylguanidine a,a-Diphenylguanidine Triethylguanidine Tribenzylguanidine.
Thesubstantially neutralized phospho-sulfurized hydrocarbon product is prepared by reaction with a basic guanidino-compound of the above type, preferably in a non-oxidizing atmosphere, by contacting the latter with the phospho-sulfurized material as such or dissolved in a suitable solvent such as naphtha at a temperature of about 100 F. to 400 F. It is generally desired to employ at least enough of the basic compound to neutralize the titratable acidity of the phospho-sulfurized hydrocarbon product. Inpractice a somewhat greater amount of basic compound is generally used since the basic compound can be reacted in proportions greater than that required for neutralization of titratable acidity. When the basic compound is added in the form of a carbonate, the completion of the reaction is indicated by a cessation of carbon dioxide evolution. A water-soluble basic compound such as 'guanidine carbonate may be dissolved in water and then contacted with the phospho-sulfurized hydrocarbon. Metal treatment may then be carried out if desired.
The metal-treated or untreated phospho-sulfurized hydrocarbon may instead be reacted with an unsaturated hydrocarbon to form the olefinic derivative by contacting the two materials at room temperature. More preferably a somewhat elevated temperature of the order of 380 F. is used with from about 0.1% to 50%, preferably about 5% to 20%, by weight of the unsaturated hydrocarbon, based on the amount of phospho-sulfurizcd hydrocarbon present.
The reaction is continued for a period of about one to about ten hours. The unreacted olefin is removed from the final product by distillation. However, in certain instances it may be desirable to employ an excess of the olefinic material or other unsaturated hydrocarbon products, then adding a sufficient quantity of sulfur to form a still more-clfective addition agent. This last step may also be made more effective by the addition of an agent commonly used in the vulcanization of rubber, such as Tuads, Captax, Tellurac, or Selenac. After-treatment with iron or copper may then be conducted, usually at a temperature'above that used in forming the olefinic derivative.
The unsaturated hydrocarbon material which is reacted with the phospho-sulfurized hydrocarbon in accordance with the present invention may be any aliphatic, cycloaliphatic, terpenic, or aliphatic-aromatic hydrocarbon containing at least one olefinic double bond carbon-to-carbon linkage in a non-aromatic group. The materials more preferably employed include the o'lefins, ,e. g., propylene, butylenes, diisobutylenes, triisobutylenes, the codimer of are-tees isobutylene and n-butylene, also cracked gasoline fractions, cracked parafiin wax, viscous olefin polymers such as medium or high molecular weight polybut ene, cyclopentene, cyclohexene, butadiene, pentadiene, isoprene, di-
pentene, a-pinene, fl-pinene, terpinolene, A2,4(8)-p-menthadiene, tyrene, and the like. Derivatives of the above described compounds containing various non-reactive substituent groups and atoms may be used to advantage, since such groups or atoms would not interfere with the reaction. Such substituted groups and atoms include nitro groups, halogen atoms, etc. Hydrocarbon materials containing from 2 to 30 carbon atoms per molecule may generally be employed. Terpenes are especially preferred.
Since the additives of the present invention are to be dissolved in mineral oils, the hydrocarbons which are reacted with sulfurand phosphorus-containing material and the materials which are further reacted with the products thus formed will be chosen with a view to provide a product which .is soluble in the oil base or which has such marginal solubility that it can be plasticized with a high molecular weight alcohol, esters, or other plasticizer.
When additives of the present invention are employed in mineral lubricating oils, they are preferably added in proportions of about 0.001 to about 20% and preferably 1.0% to about 12.0%. The proportions giving the best results will vary somewhat according to the nature of the additive and the specific purpose which the lubricant is to serve in agiven case. For commercial purposes, it is convenient to prepare concentrated oil solutions in which the amount of additive in the composition ranges from about 20% to 50% or higher by weight, and to transport and store them in such form. In preparing a lubricating oil composition for use as a crankcase lubricant, the additive concentrate is merely blended with the base oil in the required amount.
Below are given detailed description of preparations of examples of lubricating oil additives described above as well as tests in which an oil containing the additives was used as the lubricant. It is to be understood that these examples are given as illustrations of the present invention and are not to be construed as limiting the scope thereof in any way.
Example l. Preparation of P255 treated bright stocks Several pilot plant preparations of Pass-treated bright stock (a solvent extracted, dewaxed, deasphalted bright stock from Mid-Continent crude) were carried out by treating the bright stock with 10% by weight of P285 for 8-10 hours at 400 F. When the reaction was carried out in an iron (mild steel) reactor, the product was considerably more stable, as regards both the tendency to form oil-insoluble precipitates and the tendency to evolve H28, than products obtained from the same reaction in enamel or glass reactors. This is shown by the data in the table below. It should be noted that the phosphorus contents of the products prepared in glass and iron were essentially identical but the sulfur content of the material prepared in iron was significantly lower.
PROPERTIES OF Pass-TREATED BRIGHT STOCKS Reactor Material Product Analysis E I name or 11011 lass Phosphorus, wt. percent a 1. 8-2.0. Sulfur, wt. percent." 3. 7-4. 7.
Iron, wt. percent Storage stability after 1 month at room tem- Solid Prepera-ture. eipitate. Hygirogen sulfide stability 1 Pb(Ac)1 rating a ter:
24 hours at room temperature. 1U.
10 days at room temperature;
\ 1 Rated by using filter paper saturated with lead acetate (Pb (Ash) for 5 minutes exposure; no stain is 0 and jet black is 10.- i
fication of the CRC method, L-l6445, for determining the copper staining tendencies of oils, the method as modified comprising immersing a polished metallic copper strip in the oil to be tested for a period of three hours at 210 F. and noting the extent of the staining. Ratings are given on a scale of from 1 to 10 which denotes discoloration ranging from no stain to a black surface film.
B. Silver c0rr0si0n.This test involves measuring the weight change and observing the discoloration of a sterling silver strip immersed in 50cc. of the test oil for 17 hours at 325 F. The stain is rated from 0 for no discoloration to 8 for complete sulfide film. Weight changes above 1.5-2.0 mgs. are considered excessive and discolorations rating above 4 are normally considered failing although the actual limits will depend on the application for which the lubricant is designed.
C. Bronze corr0sion.-This test involved exposing a section of a bronze exhaust valve guide (attached to the end of an electrically driven stirrer) to approximately 300 cc. of the lubricating oilat 500 F. for 3 successive 4 hour periods. At the end of each period the guide section was removed, cleaned, and the weight loss determined. The total loss for the 12 hour test was calculated. Comparative data for the product prepared in the iron reactor and in enamel or glass reactors are shown in the following table:
CORROSION DATA FOR BLENDS OF Pass-BRIGHT STOCKS Example II.Guanidine salts of Pass-treated bright stocks Guanidine salts of the Pass-treated bright stocks described in Example I were prepared by neutralizing the PzSs-bright stock reaction product with 10% by weight of guanidine carbonate. This was accomplished by adding 10% by weight guanidine carbonate as a 30% aqueous solution, and stripping out the water by heating the mix ture in an open container using N2 stripping. The temperature was gradually raised until all the water was re moved, the final temperature being approximately 350 F. at which point the product was filtered. A comparsion of the materials made by neutralizing in glass equipment the products prepared in Example I is given in the following table. In this case blends of 6 wt. per cent of the guanidine salts in a solvent extracted Mid-Continent base stock having a viscosity of Saybolt seconds at 210 F. were subjected to the following bronze corrosion test at 650 F. Quarter sections of bronze exhaust valve guides were exposed to 50 cc. of oil (containing the additive under test) for 17 hours at 650 F. At the end of the test the sulfide film was removed by washing the strips with cyanide solution, and the weight loss per gram of section determined. It will be noted that the guanidine salt of the Pass-treated bright stock, where the bright stock phospho-sulfurization was carried out in iron, was much less corrosive than the corresponding product made in glass or enamel.
PROPERTIES OF GUANIDINE SALT OF PrSbTREATED BRIGHT STOCKS 1 Averages of at least 2 determinations.
Example Ill-Preparation of guanidine salt of P285- treated bright stock totally in iron In the example above only the P285 treatment was carried out in an iron reactor. In the present-example, the total reaction including the neutralization was carried out in iron. 1000 .grarnsof a solvent extracted Mid-Continent bright stock of approximately 150 :Saybolt seconds viscosity at 210 F. was charged to :an ordinary black iron (cast iron) pot sitting on a hot plate. .The bright stock was stirred and also blown with N2 and the temperature raised to 300 F. in one-half hour. At that point 300 grams of P285 were added and the temperature was raised to 450 F. The product was soaked at 450 F. for five hours and then filtered using Hy-flo filter aid while hot.
To 500 grams of the filtrate 50 grams of guanidine carbonate dissolved in 100 grams of H20 was added atabout 160 F. The temperature was gradually raised to 320- 340 F. and held at that point for two to three hours in order to remove all traces of moisture. It was againfiltered through Hy-fio. Bronze corrosion .data were-obtained for a 6.0 wt. per cent blend of this product in the same base oil and by thesame test as was used in Example II. The corrosion characteristics of the product were essentially equivalent or possibly slightly better than those of the product in Example II where only thebright stock Example IV.Treatment with iron powder A. Preparation of the PzSs-treated bright stock.-150 pounds of phenol extracted Mid-Continent'bright stock was charged to a glass-lined reactor and heated to 250- 275 F. with stirring and nitrogen blowing. pounds of P255 was added and the mixture heated to 400 F. over a period of 3 /2 hours. The reaction mixture was soaked at 400 F. for an additional 8 hours. The final product contained 1.91% phosphorus, 3.89% sulfur and had a neutralization number of 24.1.
B. Treatment of the bright-stock P285 product with iron.200 grams .of the product prepared in A above were stirred in a glass reactor with grams (10% by weight) of powdered iron. A stream of nitrogen was blown continually through the reacting materials, and after three hours at 425 F. the product wasfiltered. 150 grams of the final product were converted to the .guanidine salt by the addition of 15 grams (10% by weight) guanidine carbonate dissolved in grams .of water. The mixture was slowly heated to 320F. and held therefor one hour before it was filtered. All of the reactions were carried out in glass.
The Pass-bright stock'prepared in A above was also converted to the guanidine salt, however no iron treatment was used. In this case 130 pounds of the bright stock was treated with 13 pounds of 'guanidine carbonate 8 in 1.0 pounds of water and the addition was made at 135 F. The reaction mixture was heated to 320 F; over an eight hour period and held at 320 F. for two hours before filtering.
200 grams of this product were then treated with 20 grams (10 wt. percent) -of powdered iron for three hours at 425 F. under .a nitrogen atmosphere. A comparison of the bronze corrosion characteristics of these three final products is givenin the following table. All of the data being for 6 wt. percent blends .of the guanidine ,salts in a solvent extracted Mid-Continent base oil of 100 Saybolt viscosity at 210 F. The bronze corrosion test .used is that described in Example II.
Bronze Corrosion 17 Hours at 650'F., Wt. Loss, mg/g.
6 Wt. Percent Blends of Guanidine Salt of Untreated P2S5Bl'igllt.St0ck Guanidine Salt of Iron Treated PzSSBright Stock Iron Treated Guanidine Salt of PzssBright Stock.
Bironlz? germs on ours 6 Wt. Percent Blend at 650 F" Wt Loss, mg/g.
Guanidine Saltof Pass-Bright Stock 1.89 Copper-treated Guanidine Salt of Pass-Bright Stock 1. 42
Example VI.Treatment of P2S5-treated bright stock with copper .A. Preparation of the Pzssetreated bright st0ck.146.5 pounds of an acid-treated, clay-contracted, deasphalted, dewaxcd bright stock from Mid-Continent crude was reacted with 31.5 pounds (21%) P255 in a glass-lined reactor. The materials were heated to 400 F. over a two-hour period and the reaction was maintained at this temperature for 10 hours after which it was filtered through Hy-flo. The final product contained approximately 3% phosphorus and 6% sulfur.
B. Copper treatment-500 grams of the PzSs-treated bright stock were stirred in the presence of finely divided metallic copper at about 400 'F. A total of grams (16% by weight copper) was added portion-wise over the three-hour period, after which the product was filtered through Hy-fio. Blends (2.5 wt. percent) of the PzSs-treated bright stock and of the copper-treated P2S5- treated bright stock in an SAE 30 grade solvent extracted, Mid-Continent base stock were evaluated for HzS evolution and silver corrosion. The blends also contained 2.5 wt. percent of a 30% oil concentrate of calcium petroleum 'sulfonate. The data summarized in the following table indicate that the copper treatment made a marked impilovement in both HzS evolution and in corrosivity toward s1 ver.
greases li xample VII.Irn treatment of diisobutylene-Passtreated bright stock 1000 grams of a PzSs-treated bright stock made with P285 under the conditions given in Example IV were treated with 150 grams of close-cut diisobutylene at 300 F. for three hours. At the end of that time the untreated diisobutylene was stripped out. All of the reactions were carried out in glass.
-The diisobutylene-PzSs-bright stock reaction product was then treated with (by weight) of finely divided metallic iron at 400 F. for three hours, after which it was filtered. These materials were evaluated for hydrogen sulfide stability, and for copper and silver corrosivity as 2.5 wt. percent blends in an' SAE-30 grade solvent extracted Mid-Continent lubricating oil base stock containing 2.5 wt. percent of an oil concentrate of a calcium petroleum sulfonate.
It will be noted that in all cases the iron treatment markedly improved the material.
Example VIII .Aviati0n C. F. R. engine evaluation A sample of Pass-treated bright stock prepared in an iron reactor (Example I) was evaluated at 6.0 wt. percent in a 120 grade aviation oil in an aviation C. F. R. engine test. The results of this test show that the blend gave considerably less deposits than the base stock as illustrated in the data in the table below. The test consisted of 50 hours of operation at 1800 R. P. M. and 4 brake horsepower. The oils were rated on a demerit system where a perfectly clean surface is given a rating of zero and 10 is equivalent to the worst condition that could be expected. In the test with the base aviation oil the deposits in the critical ring zone area were very heavy (6.4 demerit) and the addition of the 6.0% Pass-treated bright stock from the iron reactor resulted in a marked improvement (2.0 demerit). Similarly improved results were obtained when using the guanidine salt of a P285- treated bright stock prepared from the Pass-treated material made in iron. These data are shown in the following table:
The products of the present invention are particularly useful as ashless detergents in aviation engine lubricating oils and the like. They may be employed in ordinary hydrocarbon lubricating oils, in heavy duty type of lubricants along with other additives of the conventional types, and with various synthetic lubricants such as those prepared by polymerization of olefins, by the reaction of oxides of carbon with hydrogen, or by other means. The conventional synthetic oils of the ester, polyester and polyether types may also be used alone or in combination with mineral lubricants as base oils. The lubricating oils may .vary considerably in viscosity and other properties, de-
. l0 pending on the use for which they are desired, but they usually range from about 35 to viscosity (Saybolt) at 210 F.
Other agents such as pour depressors, organometallic compounds, sludge dispersers, viscosity index improvers, anti-oxidants and the like may be used along with the additives of the present invention in compounding the lubricants. In addition to being employed in lubricants, the additives of the present invention may also be used in motor fuels, hydraulic fluids, cutting oils, turbine oils,
fuel oils, transformer oils, and in other petroleum products as anti-oxidants or detergents. They may also be used in gear lubricants and greases.
What is claimed is:
l. In'the process of forming a product selected from the class consisting of phospho-sulfurized, non-olefinic hydrocarbon materials and the guanidino and reactive olefinic derivatives thereof, said materials containing at least 1.0 weight percent of both phosphorus and sulfur in chemically combined form; the improvement which comprises including during at least one stage of said process a contacting with a metal selected from the class consisting of iron and copper at an elevated temperature.
2. A process as in claim 1 wherein said contacting is carried out during the phospho-sulfurization of an essentially non-olefinic hydrocarbon material with a phosphorus sulfide.
3. A process as in claim 1 wherein said contacting is carried out on said phospho-sulfurized hydrocarbon.
4. A process as in claim 1 wherein said contacting is carried out on said derivatives of said phospho-sulfurized hydrocarbon.
5. A process as in claim 1 wherein said phospho-sulfurized hydrocarbon is contacted with said metal and said derivatives are formed from the contacted product.
6. A process as in claim 1 wherein said contacting with said metal is carried out at a temperature above about 300 F.
7. A process as in claim 1 wherein said contacting is carried out with from 1 to 50 weight per cent if iron in finely divided form and the contacted material is filtered to remove solid matter.
8. In the process of forming a product selected from the class consisting of the reaction products of a lubrieating oil base stock with a phosphorus sulfide and the guanidino and reactive olefinic derivatives thereof, said product including at least 1.0 weight per cent of both phosphorus and sulfur in chemically combined form and being unstable and corrosive in character, the improvement which comprises including during at least one stage of said process a contacting with a metal selected from the class consisting of iron and copper at a temperature in the range of about 300500 F. and removing solids therefrom, whereby a substantially stable and non-corrosive product is formed.
9. A process as in claim 8 wherein said phospho-sulfurization is carried out in the presence of said metal.
10. A process as in claim 8 wherein said phosphosulfurized product is contacted with said metal.
11. A process as in claim 8 wherein said derivatives are contacted with said metal.
12. A hydrocarbon oil composition containing a detergent quantity of a product selected from the class consisting of a phospho-sulfurized substantially non-olefinic hydrocarbon materials and the guanidino and reactive olefinic derivatives thereof, said materials containing at least 1.0 weight per cent of both phosphorus and sulfur in chemically combined form; which product has been contacted during at least one stage of the preparation thereof with a metal selected from the class consisting of iron and copper at elevated temperatures and for an extended period of time, adequate to produce a substantially odorless, non-corrosive product.
13. A composition as in claim 12 in which said nongreases olefinic hydrocarbon is .a lubricating oil base stock.
14. A composition ,as in claim .13 in which saidnonolefinic hydrocarbon is a bright stock obtained from a conventionally refined petroleum residuum.
15. vA composition as in claim 12 wherein said guanidino-derivative is prepared by treatment with guanidine carbonate.
l6. Acomposition as in claim 12 wherein said reactive .olefinic derivative is prepared by treatment with ,diisobutylene.
17. A composition as in claim 12in which said phospho-sulfurized hydrocarbon is prepared by treatment with Pass.
18. A composition as in claim 12 which includes from about 0.001 to 20 weight per cent of said product.
19. A concentrate comprising essentially a lubricating oil and above about'20% of the product of claim .8.
20. In the process of forming a productselected from the class consisting of reaction products ofra substantially non-olefinic'hydrocarbon material selected from thegrtoup consisting of parafiins, aromatics, cyclo-aliphatics and petroleum fractions with a phosphorus sulfide and the guanidino and olefinic derivatives thereof, said product including at least 1.0 wt. per cent of both phosphorus and sulfur in chemically combined form and being unstable and corrosive in character, the improvement which comprises contacting at least a portion of said reaction 12 product during at least one stage of said process with a metal selected from the class consisting of iron and copper at a temperature in the range of about 300 to 500 F., whereby a substantially stable and non-corrosive product is "formed.
21. In the process of forming a reaction product of a solvent extracted bright stock with phosphorus pentasulthis at atempemture of about 200 to 600 F. in a nonoxidizing atmosphere, said product having at least about 1.0 wt. per cent of both sulfur and phosphorus in chemically combined vform, .the improvement which comprises contactingat least a'portion of said reaction product during atleast one. stage of said process with a metal selected from the group consisting of iron and copper at a tempcrature-inthe rangeof about 300 to 500 Frfor about 0.5 to 1-0 hours.
References Cited in the file of this patent UNITED STATES PATENTS 2,206,151 Bennett July 2, 1940 2,315,529 Kelso Apr. 6, 1943 2,379,312 May ,June .26, 1945 2,381,907 Hughes .et al Aug. 14, 1945 2,424,402 Loane et a1 July 22, 1947 2,443,823 Holtv June 22, 1948 2,460,041 Sparks et al. Jan. 25, 1949 2,560,543 Bartleson July 17, 1951

Claims (1)

12. A HYDROCARBON OIL COMPOSITION CONTAINING A DETERGENT QUANTITY OF A PRODUCT SELECTED FROM THE CLASS CONSISTING OF A PHOSPHO-SULFURIZED SUBSTANTIALLY NON-OLEFINIC HYDROCARBON MATERIALS AND THE GUANIDINO AND REACTIVE OLEIFINIC DERIVATIVES THEREOF, SAID MATERIALS CONTAINING AT LEAST 1.0 WEIGHT PER CENT OF BOTH PHOSPHORUS AND SULFUR IN CHEMICALLY COMBINED FORM; WHICH PRODUCT HAS BEEN CONTACTED DURING AT LEAST ONE STAGE OF THE PREPARATION THEREOF WITH A METAL SELECTED FROM THE CLASS CONSISTING OF IRON AND COPPER AT ELEVATED TEMPERATURES AND FOR AN EXTENDED PERIOD OF TIME, ADEQUATE TO PRODUCE A SUBSTANTIALLY ODORLESS, NON-CORROSIVE PRODUCT.
US2734863D Properties of guanidine salt of pjst-treated Expired - Lifetime US2734863A (en)

Publications (1)

Publication Number Publication Date
US2734863A true US2734863A (en) 1956-02-14

Family

ID=3444322

Family Applications (1)

Application Number Title Priority Date Filing Date
US2734863D Expired - Lifetime US2734863A (en) Properties of guanidine salt of pjst-treated

Country Status (1)

Country Link
US (1) US2734863A (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2935390A (en) * 1954-01-29 1960-05-03 Ethyl Corp Fuel additives

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2206151A (en) * 1936-01-15 1940-07-02 Mid Continent Petroleum Corp Process of sulphurizing oils
US2315529A (en) * 1941-03-24 1943-04-06 Standard Oil Co Phosphorus sulphide-hydrocarbon reaction product
US2379312A (en) * 1944-07-15 1945-06-26 Sinclair Refining Co Reaction products of alkylated phenols and terpene-phosphorus sulphide
US2381907A (en) * 1940-12-21 1945-08-14 Standard Oil Co Mineral oil beneficiation
US2424402A (en) * 1944-09-14 1947-07-22 Standard Oil Co Froth flotation of sulfide ores with phosphorous-sulfide-olefin reaction product
US2443823A (en) * 1945-03-02 1948-06-22 Du Pont Sulfurized terpenes
US2460041A (en) * 1945-12-21 1949-01-25 Standard Oil Dev Co Lubricating composition
US2560543A (en) * 1951-07-17 Method of processing lubricating oil

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2560543A (en) * 1951-07-17 Method of processing lubricating oil
US2206151A (en) * 1936-01-15 1940-07-02 Mid Continent Petroleum Corp Process of sulphurizing oils
US2381907A (en) * 1940-12-21 1945-08-14 Standard Oil Co Mineral oil beneficiation
US2315529A (en) * 1941-03-24 1943-04-06 Standard Oil Co Phosphorus sulphide-hydrocarbon reaction product
US2379312A (en) * 1944-07-15 1945-06-26 Sinclair Refining Co Reaction products of alkylated phenols and terpene-phosphorus sulphide
US2424402A (en) * 1944-09-14 1947-07-22 Standard Oil Co Froth flotation of sulfide ores with phosphorous-sulfide-olefin reaction product
US2443823A (en) * 1945-03-02 1948-06-22 Du Pont Sulfurized terpenes
US2460041A (en) * 1945-12-21 1949-01-25 Standard Oil Dev Co Lubricating composition

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2935390A (en) * 1954-01-29 1960-05-03 Ethyl Corp Fuel additives

Similar Documents

Publication Publication Date Title
US2850453A (en) Corrosion inhibited oil compositions
US2719125A (en) Oleaginous compositions non-corrosive to silver
US2765289A (en) Corrosion inhibitors and compositions containing the same
US2736706A (en) Lubricant containing a phosphorus acid ester-aldehyde condensation product
US2805203A (en) Addition agent for oil compositions and the like
US2467713A (en) Lubricating oil composition
US2658062A (en) Mineral oil additive
US2783204A (en) Corrosion preventing agent
US2733235A (en) Table ii
US2783202A (en) Corrosion preventing agent
US2528732A (en) Reaction products of diesters of dithiophosphoric acid and mineral oil compositions containing the same
US2743235A (en) Mineral oil composition
US2368000A (en) Lubricating compositions
US2905683A (en) Ether containing esters of dithiophosphoric acid and salts thereof
US2354536A (en) Lubricating oil composition
US2346808A (en) Lubricant
US2768999A (en) Phosphosulfurized hydrocarbons and production thereof
US2689258A (en) Reaction of terpenes with thiophosphorous acid esters and products thereof
US2530339A (en) Compounded petroleum hydrocarbon products
US2409726A (en) Lubricant composition
US2734863A (en) Properties of guanidine salt of pjst-treated
US2972579A (en) Oil compositions having reduced foaming tendencies
US2799652A (en) Corrosion resistant composition
US2480664A (en) Lubricating oil composition
US2465902A (en) Stabilized liquid petroleum hydrocarbon