Classifications

• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C321/00—Thiols, sulfides, hydropolysulfides or polysulfides
• • 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
  • C10M3/00—Liquid compositions essentially based on lubricating components other than mineral lubricating oils or fatty oils and their use as lubricants; Use as lubricants of single liquid substances
• • 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
  • C10M2219/08—Thiols; Sulfides; Polysulfides; Mercaptals
  • C10M2219/082—Thiols; Sulfides; Polysulfides; Mercaptals containing sulfur atoms bound to acyclic or cycloaliphatic carbon atoms
  • C10M2219/086—Thiols; Sulfides; Polysulfides; Mercaptals containing sulfur atoms bound to acyclic or cycloaliphatic carbon atoms containing sulfur atoms bound to carbon atoms of six-membered aromatic rings
• • 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
  • C10M2219/08—Thiols; Sulfides; Polysulfides; Mercaptals
  • C10M2219/082—Thiols; Sulfides; Polysulfides; Mercaptals containing sulfur atoms bound to acyclic or cycloaliphatic carbon atoms
  • C10M2219/087—Thiols; Sulfides; Polysulfides; Mercaptals containing sulfur atoms bound to acyclic or cycloaliphatic carbon atoms containing hydroxy groups; Derivatives thereof, e.g. sulfurised phenols
• • 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
  • C10M2219/08—Thiols; Sulfides; Polysulfides; Mercaptals
  • C10M2219/082—Thiols; Sulfides; Polysulfides; Mercaptals containing sulfur atoms bound to acyclic or cycloaliphatic carbon atoms
  • C10M2219/087—Thiols; Sulfides; Polysulfides; Mercaptals containing sulfur atoms bound to acyclic or cycloaliphatic carbon atoms containing hydroxy groups; Derivatives thereof, e.g. sulfurised phenols
  • C10M2219/089—Overbased salts
• • 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
  • C10M2221/00—Organic macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
  • C10M2221/02—Macromolecular compounds obtained by reactions of monomers involving only carbon-to-carbon unsaturated bonds
• • 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
  • C10N2040/08—Hydraulic fluids, e.g. brake-fluids

Definitions

• This invention relates to the treatment of certain polyphenyl thioethers which can also be classed as polyphenyl sulfides, which term is meant to include polyphenyl sulfides in which one or more, but not all, of the sulfur atoms have been replaced with oxygen atoms, to improve their color, odor and oxidative stability and to decrease their corrosiveness to metals.
• any lubricant or hydraulic fluid can be adjudged on the basis of many criteria such as the extent of viscosity increase, the extent of corrosion to metal surfaces in contact with the lubricant and the extent of engine deposits.
• Those skilled in the art have found various ways to improve lubricants and to thus retard or prevent the effects which shorten the useful life of a lubricant.
• small amounts of other materials, or additives can be added to lubricants in order to effect one or more of the properties of the base lubricant. Oftentimes, however, it is diflicult, especially as operating temperatures are increased, to find additives which will still perform the function for which they are added and yet not inject other problems.
• Polyphenyl thioethers have been proposed as compounds which can be employed as functional fluids in many different types of application, such as hydraulic fluids, damping fluids, synthetic lubricants and atomic reactor coolants.
• an object of this invention to provide a method for increasing the oxidation resistance of polyphenyl thioethers and compositions thereof. Another object is to provide polyphenyl thioethers and compositions thereof which have decreased metal attack and give decreased formation of engine deposits. Still another ob ject of this invention is to provide a process to improve the color and odor of polyphenyl thioethers.
• polyphenyl thioether includes a compound or physical mixture of compounds represented by the formula Aam wherein .A, A A and A are each a chalkogen having an atomic number of 8 to 16, provided at least one of A, A A and A has an atomic number of 16, X, X X X and X each are selected from the group consisting of hydrogen, alkyl, haloalkyl, halogen, arylalkyl and substituted arylalkyl, L, m and n are whole numbers each having a value of from O to 8 and a is a Whole number having a value of from 0 to 1 provided that when a is 0, m is a whole number having a value of from 1 to 2.
• Typical examples of alkyl and substituted alkyl radicals are given below. Examples of such polyphenyl thioethers are:
• n is a whole number from 0 to 6
• a and A are each selected from oxygen and sulfur W er -mi s.
• x and y are whole numbers from 0 to 3 and the sum of x+y is from 1 to 6 and A and A are each selected from oxygen and sulfur but at least one of A and A is sulfur.
• polyphenyl thioethers are:
• a typical ex ample of a mixture of polyphenyl thioethers is one which contains by weight from about 45% to about 55% 4 m-phenoxyphenyl m-phenylmercaptophenyl sulfide, from about 25% to about 35% bis(m-phenylmercaptophenyl) sulfide and from about 18% to about 25% bis(m-phen oxyphenyl) sulfide.
• Preferred polyphenyl thioethers of this invention are mixtures of m-bis(phenylmercapto)benzene and certain other materials which have properties that make them well suited for the uses disclosed above and particularly those applications, such as jet engine lubricants, requiring high temperatures, thermal and oxidative stability and wide liquid range.
• Such other materials can advantageously be employed in amounts of from about 20 to about 200 parts by weight per parts of m-bis(phenylmercapto)benzene.
• the other materials contemplated to be used with m-bis (phenylmercapto)benzene to provide such mixtures are as follows:
• cer tain more limited compositions are preferred because of wider liquid range and in many cases unexpectedly low evaporation losses as well as other properties which make such compositions well suited for lubricants for jet engines.
• the more limited, preferred compositions referred to are listed in Table I below.
• m-B is (phenylmereapto)benzene 65-35 3-phenoxy-3-phenylmercaptodiphenyl sulfide- -65 4.
• m-Bis (phenylmereapt 0)benzene 66-45 m-B is (phenylmercaptophenyl) sulfide.-. 18- 6 m-Bis(phenoxy)diphenyl sulfide -27 5 m-Bis(pheuylmereapto)benzene -45 m-Bis (phenylmerca tophenyl) sulfide 20 6 8phenoxy-3-pheny mercaptodiphenyl sulfide.
• the contacting of the fluid can be effected by means known to the art for contacting liquids with solids or gases, e.g., by agitating a mixture of the fluid and the metal or gas; by passing the fluid through a packed column of the metal or by sparging the oxygen containing gas through the fluid.
• contact is intended to mean the use of force which acts upon either the liquid, metal or oxygen containing gas. Examples of such force are agitation'of the fluid and the sparging of the oxygen containing gas through the fluids.
• the fluid can be recovered after treatment by means known to the art for separating liquids from solids as by filtration or by distilling the liquid from the treatment vessel under reduced pressure.
• the improvements in the fluid properties obtained by the process of this invention are unaifected by the concentration of the metal, the time of contact or the temperature; however, it should be realized that there are minimum values of concentration, time and temperature below which the process of this invention becomes impractical.
• a minimum concentration of metal of about 0.01% by weight of polyphenyl thioether to be treated should be used.
• the benefits obtained are effected, by particle size. The extent of the benefit obtained appears to increase as the particle size of the metal decreases.
• the length of time of contact will vary depending upon variances in the particle size but a minimum time of about one hour at about 25 C. should be used. In general, times in the order of 1 to 48 hours are suflicient for most conditions.
• the temperature at which the process of this invention is carried out can vary from about 25 C. to 350 C. or higher.
• the choice of a particular temperature will be dictated, for example, by time available, by the facili ties available, particle size and amount of the metal and the characteristics of the fluid being treated.
• a contact period of from about 1 to 5 hours at temperatures in the range of about 100 C. to about 300 C. provide the optimum efficiency of equipment and benefit to the fluid.
• potassium is most preferred in the process of this invention because of its low cost and general availability in many forms. More particularly potassium powder has been found to be best suited for the process of this invention although if the process is operated at temperatures above the melting point of the metal the initial form is inconsequential.
• EXAMPLE 1 Into a suitable boiling flask equipped with temperature sensing means, a distillation column and means for agitating the contents there were charged 150.0 grams of m-bis(phenylmercapto)benzene and 0.15 gram of potassium metal. The mixtures was heated under nitrogen to about 200 C. and held at about that temperature for two hours during which time the mixture was agitated. The metal was separated from the fluid by filtration through a course glass filter. The thus treated fluid had very little odor as compared to the untreated fluid and had a comparatively lighter color.
• EXAMPLE 2 In a suitable boiling flask equipped as described in Example 1, 150 grams of 3,3'-bis(phenylmercapto) diphenyl ether is contacted with potassium metal in the manner of Example 1, except the temperature is 25 C. and the contact time is 24 hours. A fluid having improved odor, color and oxidative stability is obtained.
• fluid A Separate samples of m-bis-(phenylmercapto) benzene, hereinafter designated as fluid A, were treated by contacting them with other metals of this invention in the manner of Example 1.
• fluid B a fluid hereinafter designated fluid B, consisting by weight of about 50% m-bis(phenylmercapt0)benzene, 11% m-bis (phenoxy)diphenyl sulfide, 15% m-bis(phenylmercaptophenyl) sulfide and 24% 3-phenoxyphenyl 3'-phenylmercaptodiphenyl sulfide was treated by contacting separate samples with potassium.
• the results of the treatments are reported below in Table II. In each case results similar to that stated in Example 1 were obtained with regard to odor.
• the metal specimens used were steel, copper, silver, titanium, magnesium alloy and aluminum alloy. However, only the results upon copper and silver are reported since the untreated compositions tested had essentially no effect on steel, magnesium alloy, titanium and aluminum alloy.
• Viscosity measurements were made according to ASTM Method D-445-S3T using a Cannon-Fenske modified Ostwald viscosimeter. The percent viscosity increase was determined by measuring the viscosity of the samples before and after the test, dividing the difference by the original viscosity and multiplying the quotient by 100. The corrosiveness to metals was determined by weighing metal specimens of known size before and after the test.
• EXAMPLE 10 Into a suitable flask equipped with temperature sensing means, a distillation column, heating means and means for introducing gas there was placed 1000 grams of mbis(phenylmercapto)benzene which was then heated to a temperature of about 200 C. A small amount of low boiling material was removed at about 185 C. Air was sparged into the fluid through a tube extending to the bottom of the flask for a period of 16 hours at a rate of 175 ft. /hrs. while the temperature was maintained at about 200 C. The fluid was then distilled from the flask at a temperature range of 187 C. to 193 C. and the oxidative stability of the fluid was determined according to the above described procedure. Accordingly, the fluid was found to have a viscosity increase at C. of 3.6% whereas another sample of the test fluid, treated as above except for air sparging was found to have a viscosity increase at 100 C. of 8.5%.
• Example 8 Similar results can be obtained by employing the procedure of Example 8 but at temperatures of from 25 C. to 300 C. or above. Contact time of from 1 to 24 hours can be employed and gas flow rate regulated to suit the equipment used and desired contact time. Thus, gas flow rate can range from 50 to 500 ft. /hrs. but usually range from 200 ft. /hrs. over a period of from 2 to 8 hours at a temperature of from about 150 C. to 250 C.
• Contact time can be reduced by employing oxygen enriched air.
• any inert carrier gas can be employed in admixture with oxygen.
• gases such as carbon dioxide, nitrogen or helium containing oxygen in the range of from 5% to 50%, by volume can be employed.
• a process for improving the oxidative stability and color of polyphenyl thioethers which comprises contacting a polyphenyl thioether in the liquid phase at a temperature of at least 25 C. with a contacting agent selected from the group consisting of alkali metals wherein the alkali metal is present in an amount of at least 0.01% by weight of said polyphenyl thioether and an oxygen containing gas wherein oxygen is present in amounts of from about 5% to about 50% by volume and is bubbled through said polyphenyl thioether.
• a contacting agent selected from the group consisting of alkali metals wherein the alkali metal is present in an amount of at least 0.01% by weight of said polyphenyl thioether and an oxygen containing gas wherein oxygen is present in amounts of from about 5% to about 50% by volume and is bubbled through said polyphenyl thioether.
• A, A A and A are each a chalkogen having an atomic number of 8 to 16, provided at least one of A, A A and A has an aromatic number of 16, X, X X X and X each are selected from the group con sisting of hydrogen, alkyl, haloalkyl, halogen, arylalkyl and substituted arylalkyl, L, m and n are whole numbers each having a value of from 0 to 8 and a is a while number having a value of from 0 to 1 provided that when a is 0, m is a whole number having a value of from 1 to 2.
• nL/Ll LV in where m is a whole number from 0 to 6, A and A are each independently selected from the group consisting of oxygen and sulfur provided at least one of A and A is sulfur.
• R is a phenyl group
• R is a phenylene group
• Y and Y are each selected from the group consisting of oxygen and sulfur provided at least one of Y and Y is sulfur and c is a whole number from 1 to 5 and (2) mixtures of (1).

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• Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
• Chemical Kinetics & Catalysis (AREA)
• General Chemical & Material Sciences (AREA)
• Oil, Petroleum & Natural Gas (AREA)
• Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
• Lubricants (AREA)

Applications Claiming Priority (1)

Publications (1)

Family

ID=24814635

Family Applications (1)

Country Status (6)

Citations (2)

• 1968
  • 1968-01-26 US US700728A patent/US3532758A/en not_active Expired - Lifetime
  • 1968-12-31 FR FR1604341D patent/FR1604341A/fr not_active Expired
• 1969
  • 1969-01-24 DE DE19691903596 patent/DE1903596A1/de active Pending
  • 1969-01-24 BE BE727357D patent/BE727357A/xx unknown
  • 1969-01-24 GB GB4222/69A patent/GB1209435A/en not_active Expired
  • 1969-01-25 JP JP44005057A patent/JPS4925254B1/ja active Pending

Patent Citations (2)

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