US2866757A - Lubricants containing deposit control additives - Google Patents

Lubricants containing deposit control additives Download PDF

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US2866757A
US2866757A US567435A US56743556A US2866757A US 2866757 A US2866757 A US 2866757A US 567435 A US567435 A US 567435A US 56743556 A US56743556 A US 56743556A US 2866757 A US2866757 A US 2866757A
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glycol bis
carbonate
glycol
polymethylene
glycol ether
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US567435A
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Stanley R Newman
Robert Y Heisler
Alpert Norman
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Texaco Inc
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Texaco Inc
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    • 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
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/02—Hydroxy compounds
    • C10M2207/023—Hydroxy compounds having hydroxy groups bound to carbon atoms of six-membered aromatic rings
    • C10M2207/027—Neutral salts thereof
    • 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
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/28—Esters
    • C10M2207/282—Esters of (cyclo)aliphatic oolycarboxylic 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
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/28—Esters
    • C10M2207/30—Complex esters, i.e. compounds containing at leasst three esterified carboxyl groups and derived from the combination of at least three different types of the following five types of compounds: monohydroxyl compounds, polyhydroxy xompounds, monocarboxylic acids, polycarboxylic acids or hydroxy carboxylic acids
    • C10M2207/302—Complex esters, i.e. compounds containing at leasst three esterified carboxyl groups and derived from the combination of at least three different types of the following five types of compounds: monohydroxyl compounds, polyhydroxy xompounds, monocarboxylic acids, polycarboxylic acids or hydroxy carboxylic acids derived from the combination of monocarboxylic acids, dicarboxylic acids and dihydroxy compounds only and having no free hydroxy or carboxyl groups
    • 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
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/28—Esters
    • C10M2207/30—Complex esters, i.e. compounds containing at leasst three esterified carboxyl groups and derived from the combination of at least three different types of the following five types of compounds: monohydroxyl compounds, polyhydroxy xompounds, monocarboxylic acids, polycarboxylic acids or hydroxy carboxylic acids
    • C10M2207/304—Complex esters, i.e. compounds containing at leasst three esterified carboxyl groups and derived from the combination of at least three different types of the following five types of compounds: monohydroxyl compounds, polyhydroxy xompounds, monocarboxylic acids, polycarboxylic acids or hydroxy carboxylic acids derived from the combination of monohydroxy compounds, dihydroxy compounds and dicarboxylic acids only and having no free hydroxy or carboxyl groups
    • 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
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/28—Esters
    • C10M2207/34—Esters having a hydrocarbon substituent of thirty or more carbon atoms, e.g. substituted succinic acid 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
    • C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
    • C10M2209/02—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M2209/08—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to a carboxyl radical, e.g. acrylate type
    • C10M2209/084—Acrylate; Methacrylate
    • 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
    • C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
    • C10M2209/10—Macromolecular compoundss obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M2209/103—Polyethers, i.e. containing di- or higher polyoxyalkylene groups
    • 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
    • C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
    • C10M2209/10—Macromolecular compoundss obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M2209/103—Polyethers, i.e. containing di- or higher polyoxyalkylene groups
    • C10M2209/104—Polyethers, i.e. containing di- or higher polyoxyalkylene groups of alkylene oxides containing two carbon atoms only
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
    • C10M2209/10—Macromolecular compoundss obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M2209/103—Polyethers, i.e. containing di- or higher polyoxyalkylene groups
    • C10M2209/105—Polyethers, i.e. containing di- or higher polyoxyalkylene groups of alkylene oxides containing three carbon atoms only
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
    • C10M2209/10—Macromolecular compoundss obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M2209/103—Polyethers, i.e. containing di- or higher polyoxyalkylene groups
    • C10M2209/106—Polyethers, i.e. containing di- or higher polyoxyalkylene groups of alkylene oxides containing four carbon atoms only
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
    • C10M2209/10—Macromolecular compoundss obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M2209/103—Polyethers, i.e. containing di- or higher polyoxyalkylene groups
    • C10M2209/107—Polyethers, i.e. containing di- or higher polyoxyalkylene groups of two or more specified different alkylene oxides covered by groups C10M2209/104 - C10M2209/106
    • 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
    • C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
    • C10M2209/10—Macromolecular compoundss obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M2209/11—Complex polyesters
    • C10M2209/111—Complex polyesters having dicarboxylic acid centres
    • 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
    • C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
    • C10M2209/10—Macromolecular compoundss obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M2209/11—Complex polyesters
    • C10M2209/112—Complex polyesters having dihydric acid centres
    • 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
    • C10M2219/06—Thio-acids; Thiocyanates; Derivatives thereof
    • 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
    • C10M2221/04—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M2221/043—Polyoxyalkylene ethers with a thioether group
    • 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
    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/08—Resistance to extreme temperature
    • 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
    • C10N2040/12—Gas-turbines
    • 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
    • C10N2040/12—Gas-turbines
    • C10N2040/13—Aircraft turbines

Definitions

  • This invention relates to a lubricating oil containing a novel class of additives which act to control deposits in the combustion zone and to minimize the effects of deposits resulting from the combustion of the fuel particularly under low temperature conditions. More specifically, this invention discloses that superior lubricating oils from the standpoint of removal of low temperature deposits, are obtained by addition of a minor amount of polymethylene glycol bis(glycol ether carbonate) of prescribed composition.
  • the subject application involves the discovery that the addition of these polymethylene glycol bis(glycol ether carbonates) to a lubricating oil produces a lubricant marked by the ability to maintain a clean engine even with dirty fuels and under low temperature conditions of operation.
  • the improved lubricating oils of this inventioircontain a polymethylene glycol bis(glycol ether carbonate) of the general formula R'O CH CH O OCOROCO (OCH CH ),,OR
  • R is a divalent symmetrical polymethylene radical containing at least 4 carbon atoms and preferably 4 to carbon atoms
  • R is an aliphatic hydrocarbon radical containing 1 to 12 carbon atoms
  • n has a value of 1 to 6.
  • the polymethylene glycol bis(glycol ether carbonates) are effective in lubricating oils in concentrations as low as 0.2 volume percent, but concentrations of 0.5 to 3.0 volume percent are normally employed. There is no critical upper limit of concentration, but economic considerations dictate that concentrations less than 5.0 volume percent polymethylene glycol bis(glycol ether carbonate) be present in the lubricating oil.
  • This invention also contemplates a process for maintaining an internal combustion engine free from deposits, particularly those formed during low temperature operation, by the presence of a polymethylene glycol bis- (glycol ether carbonate) in the combustion zone.
  • This can be effected by using a fuel containing polymethylene glycol bis(glycol ether carbonate) as disclosed in the aforedescribed co-pending application, by using a lubricant containing a polymethylene glycol bis(glycol ether carbonate) as described herein, by employing a fuel and lubricant both of which contain a polymethylene glycol bis(glycol ether carbonate) or by adding a polymethylene glycol bls( glycol ether carbonate) to either the fuel, lubricant or both during engine operation.
  • the polymethylene glycol bis(glycol ether carbonate) is added to the gasoline in an amount to constitute 0.01 to 1.0 volume percent of the fuel and/or to the lube to constitute 0.5 to 5 volume percent of the lubricating oil.
  • polymethylene glycol bis(glycol ether carbonates) which inhibit the deposit-forming tendencies of hydrocarbon fuels are readily prepared by the series of reactions described in the aforeidentified copending application.
  • the preparation involves the formation of a monochloroformate by reaction of phosgene with an ethylene or polyethylene glycol monoalkyl ether and subsequent reaction of the chloroformate with a glycol in the presence of a hydrogen chloride acceptor such as pyridine or quinoline.
  • An alternate reaction procedure involves formation of a polymethylene glycol dichloroformate by reaction of a polymethylene glycol with phosgene and subsequent reaction of the dichloroformate with a monoether of ethylene or polyethylene glycol in the presence of a hydrogen chloride acceptor.
  • the lubricating oil of this invention is effective in maintaining deposits at a low level with the result that an engine lubricated therewith shows exceptionally clean cylinder head, combustion space, valves and ring belt area.
  • the low deposit level in the engine minimizes surface ignition in all its manifestations, mainly preignition and knock.
  • the low deposit level reduces the engines octane requirement increase. Deposits on surfaces contacted by the additive-containing lubricating oil, such as piston skirts and cylinder walls, are very markedly reduced.
  • polymethylene glycol bis(glycol ether carbonates) usable in the lubricants of the invention are exemplified by the following: tetrarnethylene glycol bis(butoxyethyl v carbonate),
  • glycol carbonate ester It is necessary for the glycol carbonate ester to have the prescribed formula in order to operate effectively as deposit-control additives. If there are more than 6 ethylene oxide units, the additive becomes too water-soluble for proper functioning as a lubricant additive.
  • the polymethylene glycol bis(glycol ether carbonates) etfective in reducing deposit formation in hydrocarbon fuels are all characterized by boiling points above 650 F., a molecular weight above 300 and a carbon to oxygen weight ratio below 2.5. Apparently, the glycol carbonate ester must possess all of these properties simultaneously in order to impart deposit-forming properties to hydrocarbon fuels.
  • the polymethylene radical that is the R group contains at least 4 and preferably less than 10 carbon atoms.
  • the ethylene oxide unit e. g. the -(OCH CH group, can contain 1 to 6 units.
  • Two carbonate radicals are required since polymethylene glycol mono carbonate ester derivatives are inelfective as deposit-control additives.
  • Terminal aliphatic radicals contain 1 to 12 carbon atoms with aliphatic radicals containing 2 to 6 carbon atoms being preferred.
  • the polymethylene glycol bis(glycol ether carbonates) are effective as a deposit-control additive in a concentration of at least 0.2 volume percent of the lubricant.
  • concentration of the polymethylene glycol bis(glycol ether carbonate) usually falls between 0.5 and 3.0 volume percent of the lubricant. Since the improvement in concentrations higher than 5.0 volume percent is only marginal, a practical upper limit is about 5.0 percent level even though there is no critical upper limit. Economic considerations also dictate that the additive concentration be less than percent.
  • the polymethylene glycol bis(glycol ether carbonates) of this invention are effective in controlling deposit formation in lubricants employed in spark ignition engines, diesel motors and gas turbines.
  • the polymethylene glycol bis(glycol ether carbonates) of prescribed composition are normally used in motor oils for spark ignition engines wherein fuel derived deposits formed during low temperature operation are a particularly vexing problem.
  • Diesel lubricants containing polymethylene glycol bis(glycol ether carbonates) are effective in eliminating deposits resulting from the use of the so-' called economy diesel fuels, i. e. fuels having a high sulfur content or containing cracked or residual stocks.
  • the polymethylene glycol bis(glycol ether carbonates) are also useful as deposit control additives in gas turbine lubricants which are generally ester base lubricants.
  • the polymethylene glycol bis(glycol ether carbonates) are useful in aviation oils which lubricate reciprocating aviation engines.
  • the scope of the lubricating oils to which the polymethylene glycol bis(glycol ether carbonates) of the invention are added to form superior lubricants is broad and includes mineral oils, synthetic lubricating oils and mixtures thereof.
  • the hydrocarbon mineral oils usable in this invention can be paratfin base, naphthene base or mixed parafiinnaphthenebase distillate or residual oils.
  • Paraffin base distillate lubricating oil fractions are used in the formulation of. premium grade motor oils such as are contemplated in this invention.
  • the lubricating base generally has been subjected to solvent refining to improve its lubricity and viscosity temperature relationship as well as solvent dewaxing to remove waxy components and improve the pour of the oil.
  • mineral lubricating oils having an SUS viscosity at 100 F. be tween 50 and 1,000 may be used in the formulation of the improved lubricants of this invention but usually the viscosity range falls between 70 and 300 at 100 F.
  • the mineral lubricating oils to which the polymethylene glycol bis(glycol ether carbonates) of this invention are added usually contain other additives designed to impart other desirable properties thereto.
  • other additives designed to impart other desirable properties thereto for example,
  • the most commonly used detergent-dispersant additive is an alkaline earth metal sulfonate such as calcium petroleum sulfonate or barium petroleum sulfonate. These products are so well known as detergent-dispersant additives they require no further description. Similarly, divalent metal alkyl phenolates are widely used as detergents either alone or in combination with the alkaline earth metal petroleum sulfonates.
  • the most commonly used inhibitor and antioxidant is a divalent metal alkyl dithiophosphate which results from the neutralization of a P S -alcohol reaction product with a divalent metal or divalent metal oxide.
  • the most widely used inhibitors are barium and zinc alkyl dithiophosphates.
  • the synthetic lubricating oils are usually of the ester or ether type.
  • High molecular weight, high boiling liquid aliphatic dicarboxylic acid esters possess excellent viscosity-temperature relationships and lubricating properties and are finding ever increasing utilization in lube oils adapted for high and low temperature lubrication; esters of this type are used in the formulation of jet engine oils.
  • Examples of this class of synthetic lubricating bases are the diesters of acids such as sebacic, adipic, azelaic, alkenyl succinic, etc.; specific examples of these diesters are di-2-ethylhexyl sebacate, di-Z-ethylhexyl azelate, di-Z-ethylhexyl adipate, di-n-amyl sebacate, di-Z- ethylheXyl-n-dodecyl succinate, di-2-ethoxy-ethyl sebacate, di-2'-methoxy-2-ethoxyethyl sebacate (the methyl Carbitol diester), di-2'-ethyl-2-n-butoxyethyl sebacate (the Z-ethylbutyl Cellosolve diester), di-2-n-butoxyethyl azelate(the n-butyl Cellosolve diester) and
  • Polyester lubricants formed by a reaction of an aliphatic dicarboxylic acid of the type previously described, a glycol and a monofunctional aliphatic monohydroxy alcohol or an aliphatic monocarboxylic acid in specified moi ratios are also employed as the synthetic lubricating base in the compositions of this invention; polyesters of this type are described in U. S. 2,628,974. Polyesters formed by reaction of a mixture containing specified amounts of dipropylene glycol, sebacic acid and Z-ethylhexanol and of a mixture containing adipic acid, diethylene glycol and 2-ethylhexanoic acid illustrate this class of synthetic polyester lubricating bases.
  • Polyalkylene ethers as illustrated by polyglycols are also used as the lubricating base in the compositions of this invention.
  • Polyethylene glycol, polypropylene glycol, polybutylene glycols and mixed polyethylene-polypropylene glycols are examples of this class of synthetic lubricat ing bases.
  • the sulfur analogs of the above-described diesters, polyesters and polyalkylene ethers are also used in the formulation of the lubricating compositions of this invention.
  • Dithioesters are exemplified by di-2'ethylhexyl thiosebacate and di-n-octyl thioadipate;
  • polyethylene thioglycol is an example of the sulfur analogs of the polyalkylene glycols;
  • sulfur analogs of polyesters are exemplified by the reaction product of adipic acid, thioglycol and 2-ethylhexyl mercaptan.
  • This merit system involves visual examination of the engine part in question and their rating according to deposits by comparison with standards which have assigned ratings. For example, a rating of 10 on piston skirt designates a perfectly clean piston while a rating of zero represents the worst condition. Similarly, a rating of 100 on total engine deposits represents a perfectly clean engine, etc.
  • Base fuel A used in this test had an 87.0 ASTM research octane rating containing 2.90 ml. of TEL per gallon, had an API gravity or 58.0 and a boiling range between 106 and 396 F.; it was negative in the copper corrosion test and had an oxidation stability in the ASTM test of 530 minutes minimum.
  • Base fuel B had a 90.5 ASTM research octane rating, containing 2.67 ml.
  • TEL per gallon had an API gravity of 59.0 and a boiling range between 93 and 395 F.; it was negative in the copper strip corrosion test and had an oxidation stability of 445 minutes minimum.
  • the base fuels also contained minor amounts of gasoline inhibitor, viz., N,N-di-secondary butyl paraphenylene di amine, lecithin, and N,N-disalicylidene-1,2-diaminopropane.
  • the reference lubricating oil was a 20-20W heavy duty oil meeting supplement I requirements.
  • This reference oil contained a methacrylate VI improver and a balanced combination of additives which impart detergent, dispersant and antioxidant properties to the oil.
  • the additive mixtures comprises a barium petroleum sulfonate and a zinc alkyl dithiophosphate in which the alkyl group is a methylcyclohexyl radical.
  • polymethylene glycol bis(alkyl carbonates) which are also disclosed as novel compounds in the aforeidentified copending application Serial No. 567,476 are ineffective deposit-control additives. It has been theorized that the ether linkage in the polymethylene glycolv bis( glycol ether carbonates) is an important factor in the removal of deposits. Whatever the explanation of the effectiveness of polymethylene glycol bis(glycol ether carbonates) and of the ineffectiveness of polymethylene glycol bis(alkyl carbonates), the results are striking.
  • a lubricating oil according to claim 1 containing 0.2 to 5.0 volume percent polymethylene glycol bis(glycol ether carbonate).
  • a lubricating oil according to claim 1 containing 0.5 to 30 volume percent polymethylene glycol bis(glycol ether carbonate).
  • R is a divalent symmetrical polymethylene radical containing at least 4 carbon atoms and preferably 4 to 10 carbon atoms
  • R is an aliphatic hydrocarbon radical containing 1 to 12 carbon atoms
  • n has a value of l to 6, in an amount sufficient to eliminate deposits formed during fuel combustion and to maintain a clean engine.
  • a lubricating oil according to claim 4 containing 0.2 to 5.0 volume percent polymethylene glycol bis(glycol ether carbonate).
  • a lubricating oil according to claim 4 containing 0.5 to 3.0 volume percent polymethylene glycol bis (glycol ether carbonate).
  • a lubricating oil according to claim 4 containing 0.2 to 5 .0 volume percent 1,5-pentamethylene glycol bis(2- ethoxyethyl carbonate).
  • a lubricating oil according to claim 4 containing 0.2 to 5.0 volume percent 1,5-pentamethylene glycol bis(2,2',2" triethoxyethyl carbonate).

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Description

LUBRICANTS CONTAINING DEPOSIT CONTROL ADDITIVES Stanley R. Newman and Robert Y. Heisler, Fishkill, and Norman Alpert, Ponghkeepsie, N. Y., assignors to The Texas Company, New York, N. Y., a corporation of Delaware No Drawing. Application February 24, 1956 Serial No. 567,435
8 Claims. (Cl. 25256) This invention relates to a lubricating oil containing a novel class of additives which act to control deposits in the combustion zone and to minimize the effects of deposits resulting from the combustion of the fuel particularly under low temperature conditions. More specifically, this invention discloses that superior lubricating oils from the standpoint of removal of low temperature deposits, are obtained by addition of a minor amount of polymethylene glycol bis(glycol ether carbonate) of prescribed composition.
As auto-mobile manufacturers annually raise the compression ratio of their engines in the race for higher horsepower, the problem of engine deposits resulting from the fuel becomes increasingly more severe. Engine deposits which find their origin in the fuel are primarily responsible for surface ignition phenomena such as preignition and octane requirement increase (ORI) which is the tendency of spark ignition engines in service to require higher octane fuels for proper performance. There are two avenues by which this problem can be attacked. One approach is through the fuel and the other approach is through the lubricating oil. In our copending application filed of even date, Serial No. 567,445, it is disclosed that superior hydrocarbon fuels from the standpoint of engine deposits result from the incorporation of polymethylene glycol bis(glycol ether carbonates) of prescribed composition. The subject application involves the discovery that the addition of these polymethylene glycol bis(glycol ether carbonates) to a lubricating oil produces a lubricant marked by the ability to maintain a clean engine even with dirty fuels and under low temperature conditions of operation.
In our copending application, Serial No. 567,476 filed of even date, now Patent No. 2,821,539, there are disclosed novel polymethylene glycol carbonates of the general formula wherein R is a divalent symmetrical polymethylene radical containing at least 4 carbon atoms, R is an aliphatic hydrocarbon radical containing 1 to 12 carbon atoms and n has a value of to 10. This invention involves the discovery that a particular group of these novel compounds, the polymethylene glycol bis( glycol ether carbonates), are deposit control lubricating oil additives.
The improved lubricating oils of this inventioircontain a polymethylene glycol bis(glycol ether carbonate) of the general formula R'O CH CH O OCOROCO (OCH CH ),,OR
wherein R is a divalent symmetrical polymethylene radical containing at least 4 carbon atoms and preferably 4 to carbon atoms, R is an aliphatic hydrocarbon radical containing 1 to 12 carbon atoms and n has a value of 1 to 6. The polymethylene glycol bis(glycol ether carbonates) are effective in lubricating oils in concentrations as low as 0.2 volume percent, but concentrations of 0.5 to 3.0 volume percent are normally employed. There is no critical upper limit of concentration, but economic considerations dictate that concentrations less than 5.0 volume percent polymethylene glycol bis(glycol ether carbonate) be present in the lubricating oil.
This invention also contemplates a process for maintaining an internal combustion engine free from deposits, particularly those formed during low temperature operation, by the presence of a polymethylene glycol bis- (glycol ether carbonate) in the combustion zone. This can be effected by using a fuel containing polymethylene glycol bis(glycol ether carbonate) as disclosed in the aforedescribed co-pending application, by using a lubricant containing a polymethylene glycol bis(glycol ether carbonate) as described herein, by employing a fuel and lubricant both of which contain a polymethylene glycol bis(glycol ether carbonate) or by adding a polymethylene glycol bls( glycol ether carbonate) to either the fuel, lubricant or both during engine operation. In the latter mode of operation, the polymethylene glycol bis(glycol ether carbonate) is added to the gasoline in an amount to constitute 0.01 to 1.0 volume percent of the fuel and/or to the lube to constitute 0.5 to 5 volume percent of the lubricating oil.
The polymethylene glycol bis(glycol ether carbonates) which inhibit the deposit-forming tendencies of hydrocarbon fuels are readily prepared by the series of reactions described in the aforeidentified copending application. In general, the preparation involves the formation of a monochloroformate by reaction of phosgene with an ethylene or polyethylene glycol monoalkyl ether and subsequent reaction of the chloroformate with a glycol in the presence of a hydrogen chloride acceptor such as pyridine or quinoline. An alternate reaction procedure involves formation of a polymethylene glycol dichloroformate by reaction of a polymethylene glycol with phosgene and subsequent reaction of the dichloroformate with a monoether of ethylene or polyethylene glycol in the presence of a hydrogen chloride acceptor.
The lubricating oil of this invention is effective in maintaining deposits at a low level with the result that an engine lubricated therewith shows exceptionally clean cylinder head, combustion space, valves and ring belt area. The low deposit level in the engine minimizes surface ignition in all its manifestations, mainly preignition and knock. In addition, the low deposit level reduces the engines octane requirement increase. Deposits on surfaces contacted by the additive-containing lubricating oil, such as piston skirts and cylinder walls, are very markedly reduced.
The polymethylene glycol bis(glycol ether carbonates) usable in the lubricants of the invention are exemplified by the following: tetrarnethylene glycol bis(butoxyethyl v carbonate),
pentamethylene glycol bis(methoxyethyl carbonate), hexamethylene glycol bis(ethoxyethyl carbonate), hexamethylene glycol bis(propoxyethyl carbonate), hexamethylene glycol bis(butoxyethoxyethyl carbonate), pentamethylene glycol bis(methoxyethoxyethyl carbonate), hexamethylene glycol bis(butoxyethoxyethyl carbonate), pentamethylene glycol bis(methoxyethoxyethyl carbonate), octamethylene glycol bis(ethoxyethyl carbonate), octamethylene glycol bis(methoxyethoxyethyl carbonate), decamethylene glycol bis(ethoxyethoxyethyl carbonate), decamethylene glycol bis(butoxyethoxyethyl carbonate), pentamethylene glycol bis(Z-buten-loxyethyl carbonate), tetramethylene glycol bis(decoxyethoxyethyl carbonate), tetramethylene glycol bis(ethoxyethoxyethyl carbonate), pentamethylene glycol bis(butoxyethoxyethyl carbonate), pentamethylene glycol bis(octoxyethoxyethyl carbonate), pentamethylene glycol bis (pentoxyethyl carbonate), heptamethylene glycol bis (pentoxyethoxyethyl carbonate).
It is necessary for the glycol carbonate ester to have the prescribed formula in order to operate effectively as deposit-control additives. If there are more than 6 ethylene oxide units, the additive becomes too water-soluble for proper functioning as a lubricant additive.
The polymethylene glycol bis(glycol ether carbonates) etfective in reducing deposit formation in hydrocarbon fuels are all characterized by boiling points above 650 F., a molecular weight above 300 and a carbon to oxygen weight ratio below 2.5. Apparently, the glycol carbonate ester must possess all of these properties simultaneously in order to impart deposit-forming properties to hydrocarbon fuels.
In summary, the following conclusions can be made as to the requirements of each section of the additive molecule for the production of a polymethylene glycol bis(glycol ether carbonate) having deposit-control properties. (l) The polymethylene radical, that is the R group contains at least 4 and preferably less than 10 carbon atoms. The ethylene oxide unit, e. g. the -(OCH CH group, can contain 1 to 6 units. (2) Two carbonate radicals are required since polymethylene glycol mono carbonate ester derivatives are inelfective as deposit-control additives. (3) Terminal aliphatic radicals contain 1 to 12 carbon atoms with aliphatic radicals containing 2 to 6 carbon atoms being preferred.
The polymethylene glycol bis(glycol ether carbonates) are effective as a deposit-control additive in a concentration of at least 0.2 volume percent of the lubricant. The concentration of the polymethylene glycol bis(glycol ether carbonate) usually falls between 0.5 and 3.0 volume percent of the lubricant. Since the improvement in concentrations higher than 5.0 volume percent is only marginal, a practical upper limit is about 5.0 percent level even though there is no critical upper limit. Economic considerations also dictate that the additive concentration be less than percent.
The polymethylene glycol bis(glycol ether carbonates) of this invention are effective in controlling deposit formation in lubricants employed in spark ignition engines, diesel motors and gas turbines. However, the polymethylene glycol bis(glycol ether carbonates) of prescribed composition are normally used in motor oils for spark ignition engines wherein fuel derived deposits formed during low temperature operation are a particularly vexing problem. Diesel lubricants containing polymethylene glycol bis(glycol ether carbonates) are effective in eliminating deposits resulting from the use of the so-' called economy diesel fuels, i. e. fuels having a high sulfur content or containing cracked or residual stocks. The polymethylene glycol bis(glycol ether carbonates) are also useful as deposit control additives in gas turbine lubricants which are generally ester base lubricants. The polymethylene glycol bis(glycol ether carbonates) are useful in aviation oils which lubricate reciprocating aviation engines. The scope of the lubricating oils to which the polymethylene glycol bis(glycol ether carbonates) of the invention are added to form superior lubricants is broad and includes mineral oils, synthetic lubricating oils and mixtures thereof.
The hydrocarbon mineral oils usable in this invention can be paratfin base, naphthene base or mixed parafiinnaphthenebase distillate or residual oils. Paraffin base distillate lubricating oil fractions are used in the formulation of. premium grade motor oils such as are contemplated in this invention. The lubricating base generally has been subjected to solvent refining to improve its lubricity and viscosity temperature relationship as well as solvent dewaxing to remove waxy components and improve the pour of the oil. Broadly speaking, mineral lubricating oils having an SUS viscosity at 100 F. be tween 50 and 1,000 may be used in the formulation of the improved lubricants of this invention but usually the viscosity range falls between 70 and 300 at 100 F.
At The mineral lubricating oils to which the polymethylene glycol bis(glycol ether carbonates) of this invention are added usually contain other additives designed to impart other desirable properties thereto. For example,
' V. I. improvers such as the polymethacrylates are nor- CELL? L C O OR L wherein R is an aliphatic radical and n is an integer having a value of more than 1.
The most commonly used detergent-dispersant additive is an alkaline earth metal sulfonate such as calcium petroleum sulfonate or barium petroleum sulfonate. These products are so well known as detergent-dispersant additives they require no further description. Similarly, divalent metal alkyl phenolates are widely used as detergents either alone or in combination with the alkaline earth metal petroleum sulfonates.
The most commonly used inhibitor and antioxidant is a divalent metal alkyl dithiophosphate which results from the neutralization of a P S -alcohol reaction product with a divalent metal or divalent metal oxide. The most widely used inhibitors are barium and zinc alkyl dithiophosphates.
The synthetic lubricating oils are usually of the ester or ether type. High molecular weight, high boiling liquid aliphatic dicarboxylic acid esters possess excellent viscosity-temperature relationships and lubricating properties and are finding ever increasing utilization in lube oils adapted for high and low temperature lubrication; esters of this type are used in the formulation of jet engine oils. Examples of this class of synthetic lubricating bases are the diesters of acids such as sebacic, adipic, azelaic, alkenyl succinic, etc.; specific examples of these diesters are di-2-ethylhexyl sebacate, di-Z-ethylhexyl azelate, di-Z-ethylhexyl adipate, di-n-amyl sebacate, di-Z- ethylheXyl-n-dodecyl succinate, di-2-ethoxy-ethyl sebacate, di-2'-methoxy-2-ethoxyethyl sebacate (the methyl Carbitol diester), di-2'-ethyl-2-n-butoxyethyl sebacate (the Z-ethylbutyl Cellosolve diester), di-2-n-butoxyethyl azelate(the n-butyl Cellosolve diester) and di-2-n-butoxy'2-ethoxyethyl-n-octyl succinate (the n-butyl Carbitol diester).
Polyester lubricants formed by a reaction of an aliphatic dicarboxylic acid of the type previously described, a glycol and a monofunctional aliphatic monohydroxy alcohol or an aliphatic monocarboxylic acid in specified moi ratios are also employed as the synthetic lubricating base in the compositions of this invention; polyesters of this type are described in U. S. 2,628,974. Polyesters formed by reaction of a mixture containing specified amounts of dipropylene glycol, sebacic acid and Z-ethylhexanol and of a mixture containing adipic acid, diethylene glycol and 2-ethylhexanoic acid illustrate this class of synthetic polyester lubricating bases.
Polyalkylene ethers as illustrated by polyglycols are also used as the lubricating base in the compositions of this invention. Polyethylene glycol, polypropylene glycol, polybutylene glycols and mixed polyethylene-polypropylene glycols are examples of this class of synthetic lubricat ing bases.
The sulfur analogs of the above-described diesters, polyesters and polyalkylene ethers are also used in the formulation of the lubricating compositions of this invention. Dithioesters are exemplified by di-2'ethylhexyl thiosebacate and di-n-octyl thioadipate; polyethylene thioglycol is an example of the sulfur analogs of the polyalkylene glycols; sulfur analogs of polyesters are exemplified by the reaction product of adipic acid, thioglycol and 2-ethylhexyl mercaptan.
The action of the polymethylene glycol bis( glycol ether carbonate) in improving the deposit-removing properties of a lubricating oil was demonstrated by a modified Chevrolet deposits testCRC EL-2-650. The laboratory engines are operated under the standard conditions of this test with the exception that crankcase oil temperatures were 10 F. lower, the water jacket temperatures were 5 F. lower, and the crankcases of the test engines were ventilated. These modifications are in every case in the direction of making the test more severe and are intended to simulate low temperature conditions wherein deposit formation is most pronounced. After the termination of each run, the engine is disassembled and its parts are evaluated by a merit system adapted from the CRCL-4 1252 test. This merit system involves visual examination of the engine part in question and their rating according to deposits by comparison with standards which have assigned ratings. For example, a rating of 10 on piston skirt designates a perfectly clean piston while a rating of zero represents the worst condition. Similarly, a rating of 100 on total engine deposits represents a perfectly clean engine, etc.
In the following table, there are shown the results obtained in the modified Chevrolet deposits test with lubricating oils containing various concentrations of polymethylene glycol bis( glycol ether carbonates) and of polymethylene glycol bis(alkyl carbonates). Base fuel A used in this testhad an 87.0 ASTM research octane rating containing 2.90 ml. of TEL per gallon, had an API gravity or 58.0 and a boiling range between 106 and 396 F.; it was negative in the copper corrosion test and had an oxidation stability in the ASTM test of 530 minutes minimum. Base fuel B had a 90.5 ASTM research octane rating, containing 2.67 ml. of TEL per gallon, had an API gravity of 59.0 and a boiling range between 93 and 395 F.; it was negative in the copper strip corrosion test and had an oxidation stability of 445 minutes minimum. The base fuels also contained minor amounts of gasoline inhibitor, viz., N,N-di-secondary butyl paraphenylene di amine, lecithin, and N,N-disalicylidene-1,2-diaminopropane.
The reference lubricating oil was a 20-20W heavy duty oil meeting supplement I requirements. This reference oil contained a methacrylate VI improver and a balanced combination of additives which impart detergent, dispersant and antioxidant properties to the oil. The additive mixtures comprises a barium petroleum sulfonate and a zinc alkyl dithiophosphate in which the alkyl group is a methylcyclohexyl radical.
TABLE I Engine cleanliness in the modified Chevrolet S-II test Concentra- Total tion of Addi- Piston Engine tive in Oil at Skirt Deposits Run Termination, Vol. Percent Base Oil (Fuel A) 4.7 77. 7 Base Oil (Fuel A) plus:
1, 5-pentamethylene glycol bis (Z-ethoxyethyl carbonate) 7. 8 82. 8 3 1, -pentamethy1ene glycol bis (2-ethylhexyl carbonate) 4. 7 70. 7 3 0 Base Oil (Fuel B) 6. 1 79. 9 Base Oil (Fuel B) plus:
1, S-pentamethylene glycol bis (2,2, 2-triethoxyethy1 carbonat 9. 7 90. 7 2. 6 1, S-pentamethylene glycol bis (n amyl carbonates) 4. 8 76.8 3. 0
The data in the foregoing table clearly show that polynethylene glycol bis(glycol ether carbonates) are effective deposit-control additives for lubricating oils. Ratings above 7.8 in piston skirt deposits and above in total engine deposits are very good results in this low temperature deposits test.
It is significant that polymethylene glycol bis(alkyl carbonates) which are also disclosed as novel compounds in the aforeidentified copending application Serial No. 567,476 are ineffective deposit-control additives. It has been theorized that the ether linkage in the polymethylene glycolv bis( glycol ether carbonates) is an important factor in the removal of deposits. Whatever the explanation of the effectiveness of polymethylene glycol bis(glycol ether carbonates) and of the ineffectiveness of polymethylene glycol bis(alkyl carbonates), the results are striking.
Obviously, many modifications and variations of the invention, as hereinbefore set forth, may be made without departing from the spiritand scope thereof and, therefore, only such limitations should be imposed as are indicated in the appended claims.
We claim:
1. A lubricating oil containing a polymethylene glycol bis(glycol ether carbonate) having a carbon to oxygen weight ratio below 2.5 and a boiling point above about 650 F. and the general formula wherein R is a divalent symmetrical polymethylene radical containing at least 4 carbon atoms and preferably 4 to 10 carbon atoms, R is an aliphatic hydrocarbon radical containing 1 to 12 carbon atoms and n has a value of 1 to 6, in an amount sufiicient to eliminate deposits formed during fuel combustion and to maintain a clean engine.
2. A lubricating oil according to claim 1 containing 0.2 to 5.0 volume percent polymethylene glycol bis(glycol ether carbonate).
. 3. A lubricating oil according to claim 1 containing 0.5 to 30 volume percent polymethylene glycol bis(glycol ether carbonate).
4. A mineral lubricating oil containing a polymethylene glycol bis(glycol ether carbonate) having a carbon to oxygen weight ratio below 2.5 and a boiling point above about 650 F. and the general formula R'O CH CH O ,,OCOROCO (OCH CH ,,OR'
wherein R is a divalent symmetrical polymethylene radical containing at least 4 carbon atoms and preferably 4 to 10 carbon atoms, R is an aliphatic hydrocarbon radical containing 1 to 12 carbon atoms and n has a value of l to 6, in an amount sufficient to eliminate deposits formed during fuel combustion and to maintain a clean engine.
5. A lubricating oil according to claim 4 containing 0.2 to 5.0 volume percent polymethylene glycol bis(glycol ether carbonate).
6. A lubricating oil according to claim 4 containing 0.5 to 3.0 volume percent polymethylene glycol bis (glycol ether carbonate).
7. A lubricating oil according to claim 4 containing 0.2 to 5 .0 volume percent 1,5-pentamethylene glycol bis(2- ethoxyethyl carbonate).
8. A lubricating oil according to claim 4 containing 0.2 to 5.0 volume percent 1,5-pentamethylene glycol bis(2,2',2" triethoxyethyl carbonate).
References Cited in the file of this patent UNITED STATES PATENTS 2,370,571 Muskat Feb. 27, 1945 2,379,249 Muskat June 26, 1945 2,379,250 Muskat June 26, 1945 2,379,252 Muskat June 26, 1945 2,651,657 Mikeska Sept. 8, 1953

Claims (1)

1. A LUBRICATING OIL CONTAINING A POLYMETHYLENE GLYCOL BIS(GLYCOL ETHER CARBONATE) HAVING A CARBON TO OXYGEN WEIGHT RATIO BELOW 2.5 AND A BOILING POINT ABOVE ABOUT 650*F. AND THE GENERAL FORMULA
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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4488982A (en) * 1980-07-23 1984-12-18 Texaco Development Corp. Low foaming nonionic polyether polycarbonate surfactants and functional fluids
US5294356A (en) * 1990-09-17 1994-03-15 Mitsui Petrochemical Industries, Ltd. Polycarbonates, uses thereof, processes for preparing and purifying same
US5476602A (en) * 1990-09-17 1995-12-19 Mitsui Petrochemical Industries, Ltd. Polycarbonates, uses thereof, processes for preparing and purifying same
US6268317B1 (en) * 1997-10-30 2001-07-31 Matsushita Electric Industrial Co., Ltd. Working fluid for refrigerating cycle equipment and the refrigerating cycle equipment using the same

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Publication number Priority date Publication date Assignee Title
US2370571A (en) * 1941-03-28 1945-02-27 Pittsburgh Plate Glass Co Preparation of carbonic acid esters
US2379250A (en) * 1941-03-28 1945-06-26 Pittsburgh Plate Glass Co Preparation of carbonic acid esters
US2379252A (en) * 1941-10-04 1945-06-26 Pittsburgh Plate Glass Co Carbonic acid esters
US2379249A (en) * 1942-11-25 1945-06-26 Pittsburgh Plate Glass Co Heat transfer medium
US2651657A (en) * 1949-05-21 1953-09-08 Standard Oil Dev Co Synthetic lubricating oil

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2370571A (en) * 1941-03-28 1945-02-27 Pittsburgh Plate Glass Co Preparation of carbonic acid esters
US2379250A (en) * 1941-03-28 1945-06-26 Pittsburgh Plate Glass Co Preparation of carbonic acid esters
US2379252A (en) * 1941-10-04 1945-06-26 Pittsburgh Plate Glass Co Carbonic acid esters
US2379249A (en) * 1942-11-25 1945-06-26 Pittsburgh Plate Glass Co Heat transfer medium
US2651657A (en) * 1949-05-21 1953-09-08 Standard Oil Dev Co Synthetic lubricating oil

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4488982A (en) * 1980-07-23 1984-12-18 Texaco Development Corp. Low foaming nonionic polyether polycarbonate surfactants and functional fluids
US5294356A (en) * 1990-09-17 1994-03-15 Mitsui Petrochemical Industries, Ltd. Polycarbonates, uses thereof, processes for preparing and purifying same
US5476602A (en) * 1990-09-17 1995-12-19 Mitsui Petrochemical Industries, Ltd. Polycarbonates, uses thereof, processes for preparing and purifying same
US5565129A (en) * 1990-09-17 1996-10-15 Mitsui Petrochemical Industries, Ltd. Polycarbonates, uses thereof, processes for preparing and purifying same
EP0877013A1 (en) * 1990-09-17 1998-11-11 Mitsui Chemicals, Inc. Polycarbonates, uses thereof, processes for preparing and purifying same
US6268317B1 (en) * 1997-10-30 2001-07-31 Matsushita Electric Industrial Co., Ltd. Working fluid for refrigerating cycle equipment and the refrigerating cycle equipment using the same

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