US2344392A - Crankcase lubricant and chemical compound therefor - Google Patents
Crankcase lubricant and chemical compound therefor Download PDFInfo
- Publication number
- US2344392A US2344392A US418326A US41832641A US2344392A US 2344392 A US2344392 A US 2344392A US 418326 A US418326 A US 418326A US 41832641 A US41832641 A US 41832641A US 2344392 A US2344392 A US 2344392A
- Authority
- US
- United States
- Prior art keywords
- dicapryl
- oil
- chemical compound
- dithiophosphoric acid
- salts
- 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
Links
- 150000001875 compounds Chemical class 0.000 title description 8
- 239000000314 lubricant Substances 0.000 title description 2
- 239000010687 lubricating oil Substances 0.000 description 18
- 239000003921 oil Substances 0.000 description 18
- 150000003839 salts Chemical class 0.000 description 14
- NAGJZTKCGNOGPW-UHFFFAOYSA-N dithiophosphoric acid Chemical compound OP(O)(S)=S NAGJZTKCGNOGPW-UHFFFAOYSA-N 0.000 description 11
- 150000002148 esters Chemical class 0.000 description 10
- 239000000203 mixture Substances 0.000 description 8
- -1 dithiophosphoric acid ester Chemical class 0.000 description 7
- 229910001385 heavy metal Inorganic materials 0.000 description 7
- 229910052751 metal Inorganic materials 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 5
- 229910052788 barium Inorganic materials 0.000 description 5
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 4
- 239000004215 Carbon black (E152) Substances 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 229930195733 hydrocarbon Natural products 0.000 description 4
- 150000002430 hydrocarbons Chemical class 0.000 description 4
- 238000006386 neutralization reaction Methods 0.000 description 4
- 159000000009 barium salts Chemical class 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000010802 sludge Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 2
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Chemical compound [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 239000003599 detergent Substances 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 150000003751 zinc Chemical class 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical class C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical class [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical class [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 241000382509 Vania Species 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910000287 alkaline earth metal oxide Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N alpha-methyl toluene Natural products CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 229910052792 caesium Chemical class 0.000 description 1
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical class [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 150000001844 chromium Chemical class 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 239000002178 crystalline material Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910003439 heavy metal oxide Inorganic materials 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- CYQAYERJWZKYML-UHFFFAOYSA-N phosphorus pentasulfide Chemical compound S1P(S2)(=S)SP3(=S)SP1(=S)SP2(=S)S3 CYQAYERJWZKYML-UHFFFAOYSA-N 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Chemical class 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 150000003138 primary alcohols Chemical class 0.000 description 1
- 229910052701 rubidium Inorganic materials 0.000 description 1
- IGLNJRXAVVLDKE-UHFFFAOYSA-N rubidium atom Chemical class [Rb] IGLNJRXAVVLDKE-UHFFFAOYSA-N 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Chemical class 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011135 tin Substances 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
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
- C10M137/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing phosphorus
- C10M137/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing phosphorus having no phosphorus-to-carbon bond
- C10M137/04—Phosphate esters
- C10M137/10—Thio derivatives
-
- 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
- C10M2219/04—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions containing sulfur-to-oxygen bonds, i.e. sulfones, sulfoxides
- C10M2219/044—Sulfonic acids, Derivatives thereof, e.g. neutral 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
- 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
- C10M2219/088—Neutral 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
- 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
- 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
- C10M2223/045—Metal containing thio derivatives
-
- 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
- C10N2010/00—Metal present as such or in compounds
- C10N2010/04—Groups 2 or 12
-
- 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
- C10N2010/00—Metal present as such or in compounds
- C10N2010/06—Groups 3 or 13
-
- 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
- C10N2010/00—Metal present as such or in compounds
- C10N2010/08—Groups 4 or 14
-
- 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
- C10N2010/00—Metal present as such or in compounds
- C10N2010/10—Groups 5 or 15
-
- 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
- C10N2010/00—Metal present as such or in compounds
- C10N2010/12—Groups 6 or 16
-
- 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
- C10N2010/00—Metal present as such or in compounds
- C10N2010/14—Group 7
-
- 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
- C10N2010/00—Metal present as such or in compounds
- C10N2010/16—Groups 8, 9, or 10
-
- 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
- C10N2040/04—Oil-bath; Gear-boxes; Automatic transmissions; Traction drives
-
- 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
- C10N2040/04—Oil-bath; Gear-boxes; Automatic transmissions; Traction drives
- C10N2040/042—Oil-bath; Gear-boxes; Automatic transmissions; Traction drives for automatic transmissions
-
- 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
- C10N2040/04—Oil-bath; Gear-boxes; Automatic transmissions; Traction drives
- C10N2040/044—Oil-bath; Gear-boxes; Automatic transmissions; Traction drives for manual transmissions
-
- 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
- C10N2040/04—Oil-bath; Gear-boxes; Automatic transmissions; Traction drives
- C10N2040/046—Oil-bath; Gear-boxes; Automatic transmissions; Traction drives for traction drives
-
- 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
- This invention relates to a new class of chemical compounds which are useful as addition agents to lubricating oils of the type known as crankcase oil; i. e. hydrocarbon oils of relatively low viscosity and pour point such as are used in the crankcases of internal combustion engines and to lubricating oils of this type containing such additives. More particularly, the invention relates to the heavy metal salts of the dicapryl ester of dithiophosphoric acid and to lubricating oils of the above type containing this class of compounds.
- heavy metal salt in the following specification and claims we mean the salts of the metallic elements of groups II to VlJI inclusive of the periodic system and especially such salts as those of the alkaline earth metals magnesium, calcium, strontium and barium and other metals such as zinc, aluminum, chromium, tin, cobalt and nickel which form water-insoluble salts with dicapryl dithiophosphate. Salts of lithium, sodium, potassium, rubidium and caesium, the alkali metals, are excluded from th invention.
- the heavy metal salts of dicapryl dithiophosphoric acid ester are water-insoluble but hydrocarbon oil-soluble compounds. Most of the compounds of this class, including all the alkaline earth metal salts are brownish-yellow solids of low melting point, whereas the zinc salt is a viscous liquid at ordinary temperatures.
- the compounds as a class are soluble in hydrocarbon oils of the type of Ill-W grade lubricating oils to the extent of -50% by weight, and are therefore well adapted for manufacture and sale in the form of lubricating oil. solutions or fairly high concentration, which can be readily blended with further amounts or oil to concentrations of 9.1-3 in which they are used.
- lubricating oil containing 0.14% of heavy metal salts of the dicapryl ester of dithiophosphoric acid possess several remarkable and unexpected properties.
- these compounds are detergents for the prevention of sludge deposits in truck. bus, aeroplane and marine gasoline and Diesel englues, and that they also possess extremely importantnon-oxidizing or antioxidant properties when compared with other metal salt detergents that have previously been used.
- these compounds possess a remarkable degree of stability against decomposition and sludge formation under the conditions of heavy duty use in lubricating oil when it is considered that they are esters of aliphatic secondary alcohols of a type that are known to be considerably less heatstable than the esters of the corresponding primary alcohols.
- Dicapryl dithiophosphoric acid is prepared by reacting capryl alcohol with phosphorous pentasulfide in the ratio of approximately 4 moles of the alcohol for each mole of Past, the reaction being carried out by heating the two ingredients.
- alkaline earth metal salts so obtained have the following probable structural formula
- the corresponding salts of metals of higher va lency, such as the aluminum and chromium salts have similar structural formulas in which three or more thiophosphoric acid ester radicals are linked through sulfur to the metal.
- crankcase oils of the heavy metal salts of the above-defined class either alone or in admixture with other ingredients, in amounts sumcient to exert sludgedispersina p perties under heavy duty service conditions.
- Th formation of sludge in crankcase oils is intimately related to the pro-- be used to'combat oxidation and decomposition n the lubricating oil, and oils containing the ieavy metal dicapryl dithiophosphates in are with either or both or these comp ntitute another important feature of our invenion.
- the corresponding zinc salt was prepared by adding 41 parts by weight of finely powdered zinc oxide to a solution of 354 parts of dicapryl dithiophosphoric acid in an alcohol-benzene mixture as ,described above.
- the product was obtained as a. thin oily liquid which was easily soluble in lubricating oil.
- Example 2 samples of the oilunder test are pouredinto these tubes and air at the rate of liters per hour is ones-sea dure are shown in the following table, wherein oil A was a solvent refined l0-W grade oil and oil B was a phenol-extracted iii-W grade oil.
- Oil A-HL6% Ba dlcapryl dithiophosphate is Oil B Z3. 5 17.17 215 1. El Oil B+0A% Ba dicapryl dlthlophosphate +22 Oil B+0.6% Ba diczipryl dithiophosphate. 27. 3 3. 02 +16 3. i9
- a lubricating oil composition comprising a crankcase oil having dissolved therein ill-3% of a heavy metal salt of the dicapryl ester of dithiophosphoric acid.
- a lubricating oil composition comprising a crankcase oil having dissolved therein (ll-3% of an alkaline earth metal salt of the dicapryl ester of dithiophosphoric acid.
- a lubricating oil composition comprising a crankcase oil having dissolved therein (Ll-3% of the barium salt of the dicapryl ester of dithiophosphoric acid.
Description
Patented Mar. 14, 1944 UNETED CRANKCASE LUBRICANT AND CHEMICAL COUND THEREFOR No Drawing. Application November 8, 1941, Serial No. 418,326
6 Claims.
This invention relates to a new class of chemical compounds which are useful as addition agents to lubricating oils of the type known as crankcase oil; i. e. hydrocarbon oils of relatively low viscosity and pour point such as are used in the crankcases of internal combustion engines and to lubricating oils of this type containing such additives. More particularly, the invention relates to the heavy metal salts of the dicapryl ester of dithiophosphoric acid and to lubricating oils of the above type containing this class of compounds. By the term heavy metal salt in the following specification and claims we mean the salts of the metallic elements of groups II to VlJI inclusive of the periodic system and especially such salts as those of the alkaline earth metals magnesium, calcium, strontium and barium and other metals such as zinc, aluminum, chromium, tin, cobalt and nickel which form water-insoluble salts with dicapryl dithiophosphate. Salts of lithium, sodium, potassium, rubidium and caesium, the alkali metals, are excluded from th invention.
The heavy metal salts of dicapryl dithiophosphoric acid ester are water-insoluble but hydrocarbon oil-soluble compounds. Most of the compounds of this class, including all the alkaline earth metal salts are brownish-yellow solids of low melting point, whereas the zinc salt is a viscous liquid at ordinary temperatures. The compounds as a class are soluble in hydrocarbon oils of the type of Ill-W grade lubricating oils to the extent of -50% by weight, and are therefore well adapted for manufacture and sale in the form of lubricating oil. solutions or fairly high concentration, which can be readily blended with further amounts or oil to concentrations of 9.1-3 in which they are used.
We have discovered that lubricating oil containing 0.14% of heavy metal salts of the dicapryl ester of dithiophosphoric acid possess several remarkable and unexpected properties. We have found that these compounds are detergents for the prevention of sludge deposits in truck. bus, aeroplane and marine gasoline and Diesel englues, and that they also possess extremely importantnon-oxidizing or antioxidant properties when compared with other metal salt detergents that have previously been used. Moreover, these compounds possess a remarkable degree of stability against decomposition and sludge formation under the conditions of heavy duty use in lubricating oil when it is considered that they are esters of aliphatic secondary alcohols of a type that are known to be considerably less heatstable than the esters of the corresponding primary alcohols.
Dicapryl dithiophosphoric acid is prepared by reacting capryl alcohol with phosphorous pentasulfide in the ratio of approximately 4 moles of the alcohol for each mole of Past, the reaction being carried out by heating the two ingredients.-
together at 95 C. with stirring for about 2 /2 hours. When the evolution of H28 has subsided the resulting dicapryl dithiophosphoric acid ester is dissolved in a mixture of absolute alcohol and benzene and suflicient heavy metal oxide is added to eil'ect neutralization. The mixture is heated to complete the neutralizatlonand a part of the solvent is evaporated to expel the water of neu- -tra1ization, whereupon the solution is filtered and the filtrate evaporated to recover the product. When an alkaline earth metal oxide is used in this manner the alkaline earth metal salts so obtained have the following probable structural formula The corresponding salts of metals of higher va lency, such as the aluminum and chromium salts have similar structural formulas in which three or more thiophosphoric acid ester radicals are linked through sulfur to the metal.
As is noted above one of the most important features of our invention resides in the addition to lubricating oils of the type of hydrocarbon crankcase oils of the heavy metal salts of the above-defined class, either alone or in admixture with other ingredients, in amounts sumcient to exert sludgedispersina p perties under heavy duty service conditions. Th formation of sludge in crankcase oils is intimately related to the pro-- be used to'combat oxidation and decomposition n the lubricating oil, and oils containing the ieavy metal dicapryl dithiophosphates in are with either or both or these comp ntitute another important feature of our invenion.
The invention will be further illustrated in letail by the following specific examples, which meant results obtained with a representative ieavy metal salt of dicapryl dithiophosphate. It should be understood, however, that the inrention in its broader aspects is not limited to base examplesl Example 1 260 parts by weight of capryl alcohol iCH: (CH2) sCH(OH) CH3] were stirred rapidly with 111 parts by weight of Finely ground Pass and heated at 80-95" C. for about 2% hours. At the end of this time practically all of the P285 was reacted and the dicapryl dithiophosphoric acid remained as a brown liquid. 354 parts by weight of the prodnot so obtained were dissolvedin a. mixture of equal parts of absolute ethyl alcohol and benzene and stirred rapidly while 77 parts by weight of powdered barium oxide were added to effect neutralization. The mixture was warmed to complete the neutralization and then heated to boiling and a part of the solvent was evaporated to expel the water of neutralization. The solution was then filtered from any traces of barium salts and the filtrate evaporated. The barium dicapryl dithiophosphate was recovered as a brownish-yellow crystalline material of low melting point, insoluble in water but soluble to the extent of about 50% in l0-W grade Pennsyl- Vania, (parafiin base) lubricating oil.
The corresponding zinc salt was prepared by adding 41 parts by weight of finely powdered zinc oxide to a solution of 354 parts of dicapryl dithiophosphoric acid in an alcohol-benzene mixture as ,described above. The product was obtained as a. thin oily liquid which was easily soluble in lubricating oil.
Example 2 samples of the oilunder test are pouredinto these tubes and air at the rate of liters per hour is ones-sea dure are shown in the following table, wherein oil A was a solvent refined l0-W grade oil and oil B was a phenol-extracted iii-W grade oil.
A. P. I. gravity Naphtha 2 2 5 Neat. oxlg ilzed insoluble CwPb ho.
Per cent Oil A 201 Oil A-HL6% Ba dlcapryl dithiophosphate is Oil B Z3. 5 17.17 215 1. El Oil B+0A% Ba dicapryl dlthlophosphate +22 Oil B+0.6% Ba diczipryl dithiophosphate. 27. 3 3. 02 +16 3. i9
This application is a continuation-in-part of our copending application, Serial No. 4015960, filed July 11, 194A.
What we claim is:
1. A solution of a heavy metal salt of the dicapryl ester of dithiophosphoric acid in lubricating oil.
2. A solution of an alkaline earth metal salt of the dicapryl ester of dithiophosphoric acid in lubricating oil.
3. A solution of the barium salt of the dicapryl ester of dithiophosphoric acid in lubricating oil.
4. A lubricating oil composition comprising a crankcase oil having dissolved therein ill-3% of a heavy metal salt of the dicapryl ester of dithiophosphoric acid.
5. A lubricating oil composition comprising a crankcase oil having dissolved therein (ll-3% of an alkaline earth metal salt of the dicapryl ester of dithiophosphoric acid.
6. A lubricating oil composition comprising a crankcase oil having dissolved therein (Ll-3% of the barium salt of the dicapryl ester of dithiophosphoric acid.
ELIWER W. COOK. WILLIAM D. THOMAS, JR.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US418326A US2344392A (en) | 1941-11-08 | 1941-11-08 | Crankcase lubricant and chemical compound therefor |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US418326A US2344392A (en) | 1941-11-08 | 1941-11-08 | Crankcase lubricant and chemical compound therefor |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US2344392A true US2344392A (en) | 1944-03-14 |
Family
ID=23657646
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US418326A Expired - Lifetime US2344392A (en) | 1941-11-08 | 1941-11-08 | Crankcase lubricant and chemical compound therefor |
Country Status (1)
| Country | Link |
|---|---|
| US (1) | US2344392A (en) |
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2420893A (en) * | 1944-01-04 | 1947-05-20 | Standard Oil Dev Co | Compounded lubricating oil |
| US2447288A (en) * | 1946-03-06 | 1948-08-17 | Gulf Oil Corp | Primary aliphatic amine salts of dialiphatic substituted mono-thiophosphoric acids |
| US2514625A (en) * | 1945-12-13 | 1950-07-11 | California Research Corp | Lubricating oil composition |
| US2579038A (en) * | 1947-12-09 | 1951-12-18 | Wakefield & Co Ltd C C | Lubricant composition |
| US2734864A (en) * | 1952-05-31 | 1956-02-14 | Stabilized lubricating compositions | |
| US2885362A (en) * | 1955-12-28 | 1959-05-05 | Pure Oil Co | Paper-machine oils |
| US2916448A (en) * | 1957-05-31 | 1959-12-08 | Sinclair Refining Co | Oxidation inhibitor-detergent material |
| US2923682A (en) * | 1957-09-17 | 1960-02-02 | Exxon Research Engineering Co | Lubricating compositions containing mixed salts |
| US2937992A (en) * | 1956-05-03 | 1960-05-24 | Sinclair Refining Co | Anti-wear lubricant |
| US2944020A (en) * | 1956-05-11 | 1960-07-05 | Sinclair Refining Co | Anti-wear lubricating oil composition |
| US2944971A (en) * | 1956-05-03 | 1960-07-12 | Sinclair Refining Co | Stable anti-corrosive lubricant composition |
| US3008900A (en) * | 1958-08-07 | 1961-11-14 | Sinclair Refining Co | Manufacture of mixed nickel and zinc dithiophosphate |
| US4368129A (en) * | 1981-04-30 | 1983-01-11 | Mobil Oil Corporation | Multifunctional lubricant additives and compositions thereof |
-
1941
- 1941-11-08 US US418326A patent/US2344392A/en not_active Expired - Lifetime
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2420893A (en) * | 1944-01-04 | 1947-05-20 | Standard Oil Dev Co | Compounded lubricating oil |
| US2514625A (en) * | 1945-12-13 | 1950-07-11 | California Research Corp | Lubricating oil composition |
| US2447288A (en) * | 1946-03-06 | 1948-08-17 | Gulf Oil Corp | Primary aliphatic amine salts of dialiphatic substituted mono-thiophosphoric acids |
| US2579038A (en) * | 1947-12-09 | 1951-12-18 | Wakefield & Co Ltd C C | Lubricant composition |
| US2734864A (en) * | 1952-05-31 | 1956-02-14 | Stabilized lubricating compositions | |
| US2885362A (en) * | 1955-12-28 | 1959-05-05 | Pure Oil Co | Paper-machine oils |
| US2937992A (en) * | 1956-05-03 | 1960-05-24 | Sinclair Refining Co | Anti-wear lubricant |
| US2944971A (en) * | 1956-05-03 | 1960-07-12 | Sinclair Refining Co | Stable anti-corrosive lubricant composition |
| US2944020A (en) * | 1956-05-11 | 1960-07-05 | Sinclair Refining Co | Anti-wear lubricating oil composition |
| US2916448A (en) * | 1957-05-31 | 1959-12-08 | Sinclair Refining Co | Oxidation inhibitor-detergent material |
| US2923682A (en) * | 1957-09-17 | 1960-02-02 | Exxon Research Engineering Co | Lubricating compositions containing mixed salts |
| US3008900A (en) * | 1958-08-07 | 1961-11-14 | Sinclair Refining Co | Manufacture of mixed nickel and zinc dithiophosphate |
| US4368129A (en) * | 1981-04-30 | 1983-01-11 | Mobil Oil Corporation | Multifunctional lubricant additives and compositions thereof |
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