US2989470A - Lubricating oil composition containing certain 2:1beta-glycol borate compounds - Google Patents
Lubricating oil composition containing certain 2:1beta-glycol borate compounds Download PDFInfo
- Publication number
- US2989470A US2989470A US783669A US78366958A US2989470A US 2989470 A US2989470 A US 2989470A US 783669 A US783669 A US 783669A US 78366958 A US78366958 A US 78366958A US 2989470 A US2989470 A US 2989470A
- Authority
- US
- United States
- Prior art keywords
- lubricating oil
- compounds
- oil
- deposits
- boron
- 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
- 239000010687 lubricating oil Substances 0.000 title claims description 20
- 239000000203 mixture Substances 0.000 title description 15
- 150000001639 boron compounds Chemical class 0.000 claims description 16
- 239000003208 petroleum Substances 0.000 claims description 3
- 239000003921 oil Substances 0.000 description 25
- 150000001875 compounds Chemical class 0.000 description 14
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 10
- 229910052796 boron Inorganic materials 0.000 description 10
- 238000002485 combustion reaction Methods 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 6
- 150000001642 boronic acid derivatives Chemical class 0.000 description 6
- 125000004432 carbon atom Chemical group C* 0.000 description 6
- 125000000217 alkyl group Chemical group 0.000 description 5
- 239000000446 fuel Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 239000000654 additive Substances 0.000 description 4
- 239000007795 chemical reaction product Substances 0.000 description 4
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 3
- 239000004327 boric acid Substances 0.000 description 3
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 230000007935 neutral effect Effects 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 229910000464 lead oxide Inorganic materials 0.000 description 2
- PIJPYDMVFNTHIP-UHFFFAOYSA-L lead sulfate Chemical compound [PbH4+2].[O-]S([O-])(=O)=O PIJPYDMVFNTHIP-UHFFFAOYSA-L 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- YEXPOXQUZXUXJW-UHFFFAOYSA-N oxolead Chemical compound [Pb]=O YEXPOXQUZXUXJW-UHFFFAOYSA-N 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- MRMOZBOQVYRSEM-UHFFFAOYSA-N tetraethyllead Chemical compound CC[Pb](CC)(CC)CC MRMOZBOQVYRSEM-UHFFFAOYSA-N 0.000 description 2
- 239000012808 vapor phase Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Chemical group CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000002199 base oil Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- HOPSCVCBEOCPJZ-UHFFFAOYSA-N carboxymethyl(trimethyl)azanium;chloride Chemical compound [Cl-].C[N+](C)(C)CC(O)=O HOPSCVCBEOCPJZ-UHFFFAOYSA-N 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 150000002009 diols Chemical class 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 150000002611 lead compounds Chemical class 0.000 description 1
- ZPPSOOVFTBGHBI-UHFFFAOYSA-N lead(2+);oxido(oxo)borane Chemical compound [Pb+2].[O-]B=O.[O-]B=O ZPPSOOVFTBGHBI-UHFFFAOYSA-N 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 230000001050 lubricating effect Effects 0.000 description 1
- 238000005461 lubrication Methods 0.000 description 1
- 125000002960 margaryl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 239000010705 motor oil Substances 0.000 description 1
- 125000001421 myristyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 231100000989 no adverse effect Toxicity 0.000 description 1
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 125000002958 pentadecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000003209 petroleum derivative Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000002516 radical scavenger Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000000754 repressing effect Effects 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000010561 standard procedure Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 125000002889 tridecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000002948 undecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
- C07F5/02—Boron compounds
- C07F5/04—Esters of boric acids
-
- 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
- C10M1/00—Liquid compositions essentially based on mineral lubricating oils or fatty oils; Their use as lubricants
- C10M1/08—Liquid compositions essentially based on mineral lubricating oils or fatty oils; Their use as lubricants with additives
-
- 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
- C10M2227/00—Organic non-macromolecular compounds containing atoms of elements not provided for in groups C10M2203/00, C10M2207/00, C10M2211/00, C10M2215/00, C10M2219/00 or C10M2223/00 as ingredients in lubricant compositions
- C10M2227/06—Organic compounds derived from inorganic acids or metal salts
- C10M2227/061—Esters derived from boron
- C10M2227/062—Cyclic esters
-
- 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
Definitions
- This invention relates to a lubricating oil composition
- a lubricating oil composition comprising the reaction product of certain fl-alkylenediols with boric acidin the ratio of two moles of the diol to tributes to the deposit but it also converts it from an essentially carbonaceous deposit to one comprising appreciable quantities of lead and lead compounds mixed therewith, such as lead sulfate, and lead oxide.
- the carbonaceous deposits act as a cementing agent for the lead deposits, and the lead deposits are more diflicult to remove than the carbon deposits.
- a deposit of this sort is more tenacious and troublesome than a purely carbonaceous deposit.
- the boron compounds incorporated in liquidleaded motor fuels are volatilizable under the combustion zone conditions, and also exist in the vapor phase in the combustion zone. If such organic boron compounds were present in the oil, they would, under the combustion hydrolysis must be high, in view of the larger amounts zone conditions, nonetheless be expected to volatilize.
- reaction products of boric acid with certain B-alkylene glycols in the proportion of one mole boric acid to two moles of the flalkyleneglycols are oilsoluble, more moisture-stable, and have low volatility, provided the glycol has at least sixcarbon atoms up to about twenty carbon atoms.
- Engines operated with lubricating oils containing such boron compounds have improved performance. The deposits are reduced. The ignition temperature of such engine deposits as remain is increased, therefore repressing surface ignition.
- reaction products in accordance with the invention are defined by the following general formula:
- R and R are fi-alkylene radicals having at least six and up to twenty carbon atoms and having the following general formula:
- R and R are both alkyL' R R R and R are selected from the group consisting of hydrogen and alkyl, provided that the total number oi carbon atoms in R and R is at least 6.
- the R and R and the Ri, R R and R radicals, when alkyl, can be straightchain or branched radicals and have .1 to -17 carbon atoms.
- R and R and R R R R and R when alkyl can be methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tertiary 'butyl, secondary butyl, amyl, iso-amyl, neopentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, heptadecyl, and octadecyl radicals, taken in suflicient number to meet the requirements of the formula for the total number of six carbon atoms.
- R and R are each methyl, at least one of R R R R and R must be at least methyl,
- one B-alkylene glycol is employed, one molecular species is obtainable from the ,B-alkylene glycol and boric acid. If two fi-alkylene glycols are employed, four m0- lecular species are possible, the two borates of each glycol and two to four mixed borates, depending on the symmetry of the glycols.
- the borate compounds of the invention are solids or liquids which are stable to moisture.
- the liquids and the solutions of the compounds in oil remain homoge neous and clear when stored in a moisture-saturated chamber for forty-eight hours at room temperature (25 0.). They are soluble in petroleum lubricating oils at very large concentrations. They are substantially involatile at crankcase temperatures.
- These compounds can be prepared by mixing the reactants in the stoichiometric 2:1 molar ratios and heating them above 60 0., up to about 150 0.; on a steam plate or hot plate, with occasional stirring, until the theoretical amount of water is lost. The loss of water is determined by the weight loss of the reaction vessel and contents.
- the reactants can be refluxed in the stoichiometric ratios in dry benzene in a flask provided with a water condenser and a water-collecting trap until the theoretical amount of water has been azeotropically distilled. This permits use of a lower temperature. The water removed isdetermined by thewater in the trap. The benzene then is removed from the reaction mixture by distillation, and the residue vacuum-distilled or recrystallized.
- the borate compounds of the invention can be used with any petroleum hydrocarbon oil of lubricating viscosity.
- the SAE viscosities for lubricating oils range from No. to No. 70.
- the neutral oils and refined oils such as the acid-treated and solvent-extracted oils, are equally useful in the compositions of the invention.
- the oils may be blended from suitable bright stocks and finished neutral or refined oils of light and heavy viscosities. It is impossible here to give a complete description of the various methods used in the preparation of lubricating oils, but reference is made to the text by Georgi entitled Motor Oils and Engine Lubrication, published by Reinhold Publishing Corporation, New York (1950), chapter V, wherein the various types of lubricating oils are discussed fully. Any of the oils mentioned therein can be employed in the compositions of the invention.
- composition of the invention is prepared simply by mixing the boron compound with the oil at room temperature.
- the boron compound is soluble in the oil, and dissolves therein either instantaneously or after a short time. No solvents are required.
- compositions were subject to the Falex E.P. test, run by the standard procedure, where the load on the bearing was increased automatically and the pressure re ported was that registered at failure.
- the wear tests were run on the same equipment using a constant pressure on the bearing.
- Petroleum lubricating oil having dissolved therein a moisture-stable organic boron compound having the formula:
- R and R are B-alkylene groups having from six to twenty carbon atoms having the structure:
- R and R both being alkyl and R R R and R being selected from the group consisting of hydrogen and alkyl, the amount of said compound based on the weight of the lubricating oil being equivalent to from 0.1 to 0.5% by weight of boron.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Lubricants (AREA)
Description
United States Patent Ofiice Patented June 20, 1961 2,989,470 LUBRICATING OIL COMPOSITION CONTAINING CERTAIN 2:1 B-GLYCOL BORATE COMPOUNDS Samuel M. Darling, Lyndhurst, and Chien-Wei Liao,
Cleveland, Ohio, assignors to The Standard Oil Company, Cleveland, Ohio, a corporation of Ohio No Drawing. Filed Dec. 30, 1958, Ser. No. 783,669
4 Claims. (Cl. 252 49.6) V
This invention relates to a lubricating oil composition comprising the reaction product of certain fl-alkylenediols with boric acidin the ratio of two moles of the diol to tributes to the deposit but it also converts it from an essentially carbonaceous deposit to one comprising appreciable quantities of lead and lead compounds mixed therewith, such as lead sulfate, and lead oxide. The carbonaceous deposits act as a cementing agent for the lead deposits, and the lead deposits are more diflicult to remove than the carbon deposits. Thus, a deposit of this sort is more tenacious and troublesome than a purely carbonaceous deposit.
The nature of the lead-carbonaceous deposits is such that they are quite difiicult to remove, once they have been built up. They are not attacked by the scavenging agents which are included in the fuel with the tetraethyl lead. Despite the fact that the amount of the deposits eventually levels 01f, after which there, is no appreciable further increase, the presence of the built-up deposits interferes considerably with the operation of the engine, and it would be desirable both'to prevent formation of deposits and to remove them after they have been formed. The disadvantageous effects of these deposits are well discussed in U.S. Patent No. 2,741,548 to Samuel M. Darling, Philip S. Fay and Lorraine S. Szabo.
It has been proposed to attack such deposits by incorporating in the liquid leaded motor fuel an organic boron compound which is soluble in the -fuel. The boron compound is thought to modify the action of the fuel in v v the engine, and to react with the deposits so that the adverse effects due to the deposits are eliminated or markedly reduced.
It is known that the carbonaceous components of the deposits in the engine are built up not only irom the gasoline but also from the oil, which enters the combustion system from the crankcase in various ways. This oil is in the liquid phase in the combustion zone of the engine, whereas the gasoline, of course, is in the vapor phase. However, it is essential that the boron compound be soluble in the medium in which it is introduced into the engine. For use in lubricating oil, the solubility must be quite high, relative to that in gasoline, because more additive is needed in the lubricating oil to obtain an effect. Moreover, the stability of the boron compound against of compound present, and the hydrolysis products must be soluble in the oil as well, since insoluble boron deposits in the crankcase and lubricated parts of the engine might be harmful and certainly would be difficult to remove.
Moreover, the boron compounds incorporated in liquidleaded motor fuels are volatilizable under the combustion zone conditions, and also exist in the vapor phase in the combustion zone. If such organic boron compounds were present in the oil, they would, under the combustion hydrolysis must be high, in view of the larger amounts zone conditions, nonetheless be expected to volatilize.
Compounds having a much higher boiling point are neces sary for use in lubricating oils. Such compounds should also be stable in the presence of moisture. Because of this, 'it hasv not been possible to incorporate-these compounds in the oil. i
It has now been determined, in accordance with the invention, that the reaction products of boric acid with certain B-alkylene glycols in the proportion of one mole boric acid to two moles of the flalkyleneglycols are oilsoluble, more moisture-stable, and have low volatility, provided the glycol has at least sixcarbon atoms up to about twenty carbon atoms. Engines operated with lubricating oils containing such boron compounds have improved performance. The deposits are reduced. The ignition temperature of such engine deposits as remain is increased, therefore repressing surface ignition. It is thought that the boron compounds react with the lead in the deposits forming lead-borate, and that this does not act catalytically to the same extent becausesit has a higher glow point than the lead oxide and lead sulfate usually present in such deposits. These additives are compatible with conventional lubricating oil additives.
The reaction products in accordance with the invention are defined by the following general formula:
where R and R are fi-alkylene radicals having at least six and up to twenty carbon atoms and having the following general formula:
Ti l R2 R4 Ra linking the radical to the group. R and R are both alkyL' R R R and R are selected from the group consisting of hydrogen and alkyl, provided that the total number oi carbon atoms in R and R is at least 6. The R and R and the Ri, R R and R radicals, when alkyl, can be straightchain or branched radicals and have .1 to -17 carbon atoms. Thus, R and R and R R R and R when alkyl, can be methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tertiary 'butyl, secondary butyl, amyl, iso-amyl, neopentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, heptadecyl, and octadecyl radicals, taken in suflicient number to meet the requirements of the formula for the total number of six carbon atoms. Thus, when R and R are each methyl, at least one of R R R and R must be at least methyl,
If one B-alkylene glycol is employed, one molecular species is obtainable from the ,B-alkylene glycol and boric acid. If two fi-alkylene glycols are employed, four m0- lecular species are possible, the two borates of each glycol and two to four mixed borates, depending on the symmetry of the glycols.
The extraordinary moisture stability of the compounds of the invention is explained by postulating the existence of a chelated structure, in which the free OH group is attached to the boron by a semicovalent bond, thus:
There is much evidence to support this structure. Since 3 this has not been definitely established, however, the compounds are not shown in this structural arrangement.
Typical of the compounds which come the invention are the following:
It has already been indicated that when one fl-glycol is employed, only one molecular species is formed, and that when a mixture of two is used, two to four molecular species are possible. It will be apparent from the above that more complex mixtures of reaction products can be obtained from mixtures of three and more p-diols. However, all of these are operative in the compositions of the invention.
The borate compounds of the invention are solids or liquids which are stable to moisture. The liquids and the solutions of the compounds in oil remain homoge neous and clear when stored in a moisture-saturated chamber for forty-eight hours at room temperature (25 0.). They are soluble in petroleum lubricating oils at very large concentrations. They are substantially involatile at crankcase temperatures.
These compounds can be prepared by mixing the reactants in the stoichiometric 2:1 molar ratios and heating them above 60 0., up to about 150 0.; on a steam plate or hot plate, with occasional stirring, until the theoretical amount of water is lost. The loss of water is determined by the weight loss of the reaction vessel and contents. AlternativelyQthe reactants can be refluxed in the stoichiometric ratios in dry benzene in a flask provided with a water condenser and a water-collecting trap until the theoretical amount of water has been azeotropically distilled. This permits use of a lower temperature. The water removed isdetermined by thewater in the trap. The benzene then is removed from the reaction mixture by distillation, and the residue vacuum-distilled or recrystallized.
The compounds numbered (2), (4), and (14) above were subjected to screening tests to determine oil solubility, moisture stability and volatility. Oil solubility was observed at a concentration of about 0.1% boron. Moisture stability was studied with both the undiluted liquid additive and an oil solution containing at least the equivalent of 0.1% boron. Samples had to remain visually unchanged with respect to homogeneity and clearness after being stored in a moisture-saturated chamber for forty-eight hours. Volatility was determined by the distillation characteristics of the compounds themselves. The data obtained appears in Table I:
The borate compounds of the invention can be used With any petroleum hydrocarbon oil of lubricating viscosity. The SAE viscosities for lubricating oils range from No. to No. 70. The neutral oils and refined oils, such as the acid-treated and solvent-extracted oils, are equally useful in the compositions of the invention. The oils may be blended from suitable bright stocks and finished neutral or refined oils of light and heavy viscosities. It is impossible here to give a complete description of the various methods used in the preparation of lubricating oils, but reference is made to the text by Georgi entitled Motor Oils and Engine Lubrication, published by Reinhold Publishing Corporation, New York (1950), chapter V, wherein the various types of lubricating oils are discussed fully. Any of the oils mentioned therein can be employed in the compositions of the invention.
Relatively large amounts of the organic borate compounds of the invention, in oils as compared to the amounts required in gasoline, are needed to give an improvement in engine performance. All proportions of the compounds are based on the amount of boron in the compound as a percent of the total oil composition, since it is the boron that is the active component in removing the deposit. At least 0.05% is the minimum. Use of amounts in excess of 0.5% usually cannot be justified economically, and excessive amounts may lower the viscosity index.
The composition of the invention is prepared simply by mixing the boron compound with the oil at room temperature. The boron compound is soluble in the oil, and dissolves therein either instantaneously or after a short time. No solvents are required.
The following examples represent in the opinion of the inventors the best embodiments of their invention:
Examples 1 to 3 Three lubricating oil compositions were prepared using a lubricating oil blend of 67% solvent-extracted neutral oil, 300 SSU at 100 F. and 33% of a solvent-extracted 6 bright stock 78 SSU at 210 F. To' the oil was added 2% of the following borate compounds:
EXAMPLE 1 om-o crave-02H. n-o-om-o-crrrou EXAMPLE 2 1 Cr s OH; CH;
When the above oils were used in the crankcase of an internal combustion engine operating for a period of over seventy-two hours on non boron-containing gasoline and the engine was then dismantled, the deposits in the combustion chamber were found to contain boron with the attendant advantages of the same in the deposit as discussed earlier.
The compositions were subject to the Falex E.P. test, run by the standard procedure, where the load on the bearing was increased automatically and the pressure re ported was that registered at failure. The wear tests were run on the same equipment using a constant pressure on the bearing.
The data showed that the oil of the invention containing the boron compound tolerated higher pressure and produced less wear than either the corresponding blend without boron or the base oil alone, thereby indicating that there would be no adverse effect by the use in crankcases of engines.
We claim:
1. Petroleum lubricating oil having dissolved therein a moisture-stable organic boron compound having the formula:
where R and R are B-alkylene groups having from six to twenty carbon atoms having the structure:
R1 R: R5
it. is. l.
the free valences being attached to oxygen, R and R both being alkyl and R R R and R being selected from the group consisting of hydrogen and alkyl, the amount of said compound based on the weight of the lubricating oil being equivalent to from 0.1 to 0.5% by weight of boron.
2. Lubricating oil in accordance with claim 1 in which the boron compound is:
3. Lubricating oil in accordance with claim 1 in which the boron compound is:
' 4. Lubricating oil in accordanccwith claim 1 in which the boron compound is:
C Hr-O References Cited in the file of this patent 8 Darling June 7, 1955 Darling et a1. Apt. 10, 1956 Thomas et a1. June 11, 1957 Garner June 17, 1958 Irish et a1. Dec. 3Q, 1958 FOREIGN PATENTS Great Britain -t. Ian. 26, 1955
Claims (1)
1. PETROLEUM LUBRICATING OIL HAVING DISSOLVED THEREIN A MOISTURE-STABLE ORGANIC BORON COMPOUND HAVING THE FORMULA:
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US783669A US2989470A (en) | 1958-12-30 | 1958-12-30 | Lubricating oil composition containing certain 2:1beta-glycol borate compounds |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US783669A US2989470A (en) | 1958-12-30 | 1958-12-30 | Lubricating oil composition containing certain 2:1beta-glycol borate compounds |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US2989470A true US2989470A (en) | 1961-06-20 |
Family
ID=25130053
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US783669A Expired - Lifetime US2989470A (en) | 1958-12-30 | 1958-12-30 | Lubricating oil composition containing certain 2:1beta-glycol borate compounds |
Country Status (1)
| Country | Link |
|---|---|
| US (1) | US2989470A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3232876A (en) * | 1961-07-21 | 1966-02-01 | Gulf Research Development Co | Boron-containing copolymers and lubricating oils containing them |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2526506A (en) * | 1947-10-29 | 1950-10-17 | Standard Oil Dev Co | Hydrocarbon lubricant containing sulfurized aliphatic borates as stabilizers |
| GB722537A (en) * | 1952-02-21 | 1955-01-26 | Shell Refining & Marketing Co | Liquid fuels for internal combustion engines |
| US2710252A (en) * | 1954-05-17 | 1955-06-07 | Standard Oil Co | Alkanediol esters of alkyl boronic acids and motor fuel containing same |
| US2741548A (en) * | 1954-10-15 | 1956-04-10 | Standard Oil Co | Leaded motor fuel containing boron compounds |
| US2795548A (en) * | 1954-06-29 | 1957-06-11 | California Research Corp | Lubricant compositions |
| US2839564A (en) * | 1952-02-21 | 1958-06-17 | Shell Dev | Cyclic esters of boric acid |
| US2866811A (en) * | 1956-04-19 | 1958-12-30 | Ethyl Corp | Esters of acyclic polyols with metaboric acid |
-
1958
- 1958-12-30 US US783669A patent/US2989470A/en not_active Expired - Lifetime
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2526506A (en) * | 1947-10-29 | 1950-10-17 | Standard Oil Dev Co | Hydrocarbon lubricant containing sulfurized aliphatic borates as stabilizers |
| GB722537A (en) * | 1952-02-21 | 1955-01-26 | Shell Refining & Marketing Co | Liquid fuels for internal combustion engines |
| US2839564A (en) * | 1952-02-21 | 1958-06-17 | Shell Dev | Cyclic esters of boric acid |
| US2710252A (en) * | 1954-05-17 | 1955-06-07 | Standard Oil Co | Alkanediol esters of alkyl boronic acids and motor fuel containing same |
| US2795548A (en) * | 1954-06-29 | 1957-06-11 | California Research Corp | Lubricant compositions |
| US2741548A (en) * | 1954-10-15 | 1956-04-10 | Standard Oil Co | Leaded motor fuel containing boron compounds |
| US2866811A (en) * | 1956-04-19 | 1958-12-30 | Ethyl Corp | Esters of acyclic polyols with metaboric acid |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3232876A (en) * | 1961-07-21 | 1966-02-01 | Gulf Research Development Co | Boron-containing copolymers and lubricating oils containing them |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US3361672A (en) | Stabilized organic compositions | |
| US3010903A (en) | Phosphate additives for hydrocarbon compositions | |
| US3046224A (en) | High barium content complex salts of sulfonic acids and petroleum fractions containing the same | |
| US3778454A (en) | Complex ester | |
| US2851417A (en) | Complex alkoxy metal salts of organic acids and lubricating and fuel compositions thereof | |
| US2866811A (en) | Esters of acyclic polyols with metaboric acid | |
| US2975135A (en) | Lubricating oil composition containing 2:1alpha-glycol borate compounds | |
| US2979459A (en) | Lubricating oil composition containing mixed 2:1alpha- and beta-glycol borate compounds | |
| US3668237A (en) | Amine salts of phosphinic acid esters | |
| US2989468A (en) | Lubricating oil composition containing 3:2beta-glycol borate compounds | |
| US3076013A (en) | Process for preparing a complex mixture of aliphatic glycol borates | |
| US2628942A (en) | Lubricating oils containing metal derivatives of cyclic imides | |
| US2432095A (en) | Lubricating composition | |
| US2989470A (en) | Lubricating oil composition containing certain 2:1beta-glycol borate compounds | |
| US2261227A (en) | Compression ignition engine fuels | |
| US3356707A (en) | Boron esters and process of preparing same | |
| US2989467A (en) | Lubricating oil composition containing 3:2alpha-glycol borate compounds | |
| US3231347A (en) | Gasolene composition containing organometallic orthophosphates | |
| US3844964A (en) | Extreme pressure lubricating oil additive | |
| US3412029A (en) | Organic compositions | |
| US3152080A (en) | Amido-bis-imidazolines in lubricating oil compositions | |
| US2989469A (en) | Lubricating oil composition containing certain 2:1beta-glycol borate compounds | |
| US2952636A (en) | Associates of inorganic metal compounds with copolymers containing a plurality of hydroxy groups | |
| US3009799A (en) | Jet fuel compositions containing alkylene biborates | |
| US3340191A (en) | Fuel and lubricant compositions |