US3785975A - Vapor space inhibited turbine oil - Google Patents
Vapor space inhibited turbine oil Download PDFInfo
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- US3785975A US3785975A US00154684A US3785975DA US3785975A US 3785975 A US3785975 A US 3785975A US 00154684 A US00154684 A US 00154684A US 3785975D A US3785975D A US 3785975DA US 3785975 A US3785975 A US 3785975A
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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
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- 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
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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
- 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
- C10M2207/026—Hydroxy compounds having hydroxy groups bound to carbon atoms of six-membered aromatic rings with tertiary alkyl groups
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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
- C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
- C10M2207/10—Carboxylix acids; Neutral salts thereof
- C10M2207/12—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms
- C10M2207/121—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of seven or less carbon atoms
- C10M2207/123—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of seven or less carbon atoms polycarboxylic
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- 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
- C10M2207/10—Carboxylix acids; Neutral salts thereof
- C10M2207/12—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms
- C10M2207/125—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of eight up to twenty-nine carbon atoms, i.e. fatty acids
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- 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
- C10M2207/10—Carboxylix acids; Neutral salts thereof
- C10M2207/12—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms
- C10M2207/129—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of thirty or more carbon atoms
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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
- C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
- C10M2207/10—Carboxylix acids; Neutral salts thereof
- C10M2207/22—Acids obtained from polymerised unsaturated acids
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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
- C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
- C10M2207/28—Esters
- C10M2207/287—Partial esters
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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
- C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
- C10M2215/22—Heterocyclic nitrogen compounds
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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
- C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
- C10M2215/22—Heterocyclic nitrogen compounds
- C10M2215/221—Six-membered rings containing nitrogen and carbon only
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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
- C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
- C10M2215/22—Heterocyclic nitrogen compounds
- C10M2215/225—Heterocyclic nitrogen compounds the rings containing both nitrogen and oxygen
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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
- C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
- C10M2215/22—Heterocyclic nitrogen compounds
- C10M2215/225—Heterocyclic nitrogen compounds the rings containing both nitrogen and oxygen
- C10M2215/226—Morpholines
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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
- C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
- C10M2215/30—Heterocyclic compounds
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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
- C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
- C10M2219/02—Sulfur-containing compounds obtained by sulfurisation with sulfur or sulfur-containing compounds
- C10M2219/024—Sulfur-containing compounds obtained by sulfurisation with sulfur or sulfur-containing compounds of esters, e.g. fats
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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
- 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
- C10M2223/043—Ammonium or amine salts thereof
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- 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
- C10N2040/135—Steam engines or turbines
Definitions
- a vapor space inhibited turbine oil comprises (1) a major amount of a mineral lubricating oil and (2) a small amount of each of (a) an alkyl phenol, e.g., 2,6-di-tertiary-butyl-4-methylphenol;
- an acid ester of (1) a dimeric acid derived from an unsaturated fatty acid and (2) a partial ester of a fatty acid and an alkitol anhydride, e.g., dimerized linoleic acid-sorbitan monooleate acid ester;
- a sulfurized monoester such as sulfurized sperm oil may also be employed.
- This invention relates to lubricating oil compositions and more particularly to compounded turbine oils adapted to prevent rusting and/ or corrosion of metal parts in the vapor space of a steam turbine.
- compositions having good lubricating characteristics and/ or good antirust and anticorrosion characteristics have been disclosed in US. Pats. Nos. 2,767,144 to R. I. Gottshall et al.; 2,786,028 to R. I. Gottshall et al.; 2,789,- 950 to R. I. Gottshall et al.; 2,789,951 to R. T. Kern et al. and 2,789,952 to T. L. Cantrell et al.
- the make-up of the lubricating compositions disclosed in the aforesaid patents are briefly set forth in the following paragraphs.
- US. Pat. No. 2,767,144 to R. I. Gottshall et al. dis closes a lubricating composition consisting essentially of a major amount of a lubricating oil and a minor amount of an acid ester of (l) a dimeric acid derived from an unsaturated fatty acid containing from 6 to 22 carbon atoms and having from 2 to 3 ethylenic linkages per molecule and (2) a partial ester of a fatty acid containing from 12 to 24 carbon atoms and an alkitol anhydride.
- US. Pat. No. 2,789,950 to R. I. Gottshall et al. discloses a lubricating composition consisting essentially of a major amount of a lubricating oil and minor amounts of each of an alkyl phenol, a substantially neutral addi tion product of isoamyl octyl acid phosphate with primary fatty amines containing from 8 to 18 carbon atoms, and an acid ester of (1) a dimeric acid derived from an unsaturated fatty acid containing from 6 to 22 carbon atoms and having from 2 to 3 ethylenic linkages per molecule and (2) a partial ester of a fatty acid containing from 12 to 24 carbon atoms and an alkitol anhydride.
- US. Pat. No. 2,789,951 to R. T. Kern et a1. discloses a lubricating composition consisting essentially of a major amount of a lubricating oil and minor amounts of each of a metal alkyl thiophosphate, an alkyl phenol, a substantially neutral addition product of isoamyl octyl acid phosphate with primary fatty amines containing from 8 to 18 carbon atoms, and an acid ester of (l) a dimeric acid derived from an unsaturated fatty acid containing from 6 to 22 carbon atoms and having from 2 to 3 ethylenic linkages per molecule and (2) a partial ester of a fatty acid containing from 12 to 24 carbon atoms and an alkitol anhydride.
- US. Pat. No. 2,786,028 to R. I. Gottshall et al. disclosesa lubricating composition consisting essentially of a major amount of a lubricating oil and minor amounts of :each of an alkyl phenol, a substantially neutral addition product of isoamyl octyl acid phosphate with a primary fatty amine containing from 8 to l8 carbon atoms, an alkenyl-substituted succinic acid anhydride wherein the alkenyl group contains from 5 to 18 carbon atoms, and an acid ester of (l) a dimeric acid derived from an un saturated fatty acid containing from 6 to 22 carbon atoms and having from 2 to 3 ethylenic linkages per molecule and (2) a partial ester of a fatty acid containing from 12 to 24 carbon atoms and an alkitol anhydride. 7 1
- lubricating compositions disclosed in the above patents in general, have good lubricating charac' teristics combined with good oxidation stability and good rust-inhibiting properties so long as the lubricating com positions are in contact with the surfaceto be lubricated, the compositions do not possess the characteristics of lubricating compositions adapted to prevent rusting and/or corrosion of metal parts in the vapor space of asteam turbine. v t
- a composition having good lubricating characteristics combined with antirust and anti corrosion properties both to metal surface in contact with the composition andto metal surfaces not in intimate contact with the composition, such as metal sur-. faces in the vapor space of a steam turbine can be 0b-' tained by incorporating in a major amount of a mineral lubricating oil a small amount of each of (a) an alkyl phenol; (b) an amine salt' of a diester of (J-phosphoric acid; (c) an alkenyl-sub'stituted succinic acid anhydride wherein the alkenyl group contains 5 to 18 carbon atornsf (d) an acid ester of (l) a dimeric acid derived from an unsaturated fatty acid containing 6 to 22 carbon atoms and having 2 to 3 ethylenic linkages per molecule and i (2) a partial ester of a fatty acid containing 12 to 24 car- 3 bon atoms and an alkitol anhydride; (e) an alky
- the mineral lubricating oil to which the other constitucuts are added is advantageously a refined or semirefined parafl'inic base oil.
- a mineral oil which has been treated with hydrogen because of its improved stability over the untreated oil, is particularly suitable as a lubricating oil base for preparing a lubricant to be used in a steam turbine.
- a preferred embodiment of the invention utilizes a mineral lubricating oil which has been treated with hydrogen whereby extensive hydrogenation of the olefinic and/or aromatic constituents present in the charge stock has been efiected.
- the hydrogen treating process may be either a hydrofinishing process or a hydrotreating process.
- the method by which a hydrogenated mineral lubricating oil is obtained is not a part of the present invention.
- the viscosity requirements of the mineral oil employed in preparing a composition of the invention will vary depending upon the end use of the lubricant. Thus, various grades of oil extending from light to extra heavy oils can be employed. Oils within this range may have viscosities of about 100 to about 2500 SUS at 100 F. If desired, a blend of oils of suitable viscosity may be employed instead of a single oil by means of which any desired viscosity may be secured.
- the mineral oil content of the composition of the invention comprises about 90 to about 99.5 percent by weight of the total composition. The particular mineral lubricating oil a well as the exact amount of such oil employed, therefore, depends upon the characteristics desired in the final composition.
- the alkyl phenol which is used in accordance with the invention is advantageously a dior tri-alkylated phenol or cresol with at least one of the alkyl groups being a tertiary alkyl group.
- the alkyl groups are preferably those containing between 3 and 12 carbon atoms. Good results can be obtained with a tri-tertiary butyl phenol or a ditertiary butyl cresol.
- Examples of the preferred alkylated phenols are 2,4,6-tri-tertiary-butylphenol and 2,6-di-tertiary-butyl-4-methylphenol.
- the alkyl phenols can be used in amounts of about 0.1 to about 5.0 percent by weight based on the weight of the total composition. The preferred amount, however, is between about 0.2 and about 1.25 percent by weight.
- the amine salt of the diester of o-phosphoric acid is conveniently prepared by neutralizing a diester of the particular phosphoric acid with approximately stoichiometric proportions of an amine of the class described herein.
- the pH of the reaction mixture be adjusted to substantially neutral, i.e., between about 5.5 and about 7.5, by controlling the amount of amine introduced into the reaction.
- a lower pH for example, of the order of 3.0 or 3.5 is satisfactory.
- the neutralization reaction normally takes place spontaneously or substantially so, with the evolution of heat. It is preferable to maintain the reaction temperature below about 180 F., cooling the reaction mixture if necessary.
- Amines which form suitable amine salts ofr the purposes of this invention are those having the general formula:
- R, R and R are hydrogen or organic radicals.
- suitable salts for the purpose of this invention are formed by primary, secondary and tertiary amines whose organic substituents can be either aliphatic radicals, including saturated, unsaturated, cyclic, branched chain and straight chain radicals or aromatic radicals.
- the invention includes the use of oilsoluble organic phosphate salts of primary, secondary and tertiary, straight or branched chain alkyl, alkenyl and alkadienyl amines, and primary, secondary, and tertiary cycloalkyl amines, heterocyclic amines, and primary, secondary and tertiary aryl amines, including alkaryl and aralkyl amines.
- amines are butyl, tributyl, octyl, dioctyl, dodecyl, octadecyl, octadecadienyl, cyclopentyl, cyclohexyl, dicyclohexyl, cycloheptyl and abietyl (rosin) amines, aniline, N-methyl aniline, N,N-dimethyl aniline, toluidine, xylidine, pyridine, piperidine and the like.
- Commercial mixtures of amines, such as cocoamine form highly satisfactory phosphate salts of the kind included by the invention.
- Cocoamine is a mixture of amines prepared from coconut oil fatty acids and contains a predominant amount of n-dodecyl amine (lauryl amine), together with minor amounts of n-octyl, n-decyl, n-tetradecyl, n-hexadecyl, n-octadecyl and n-octadecenyl amines.
- Another suitable commercial amine mixture is tallow amine, a mixture of C n-alkyl and alkenyl amines derived from animal tallow fatty acids.
- salts of amines containing hydrocarbon substituents are preferred, salts of amines whose substituents contain elements such as oxygen, halogens, sulfur, nitrogen or phosphoru which do not adversely affect the oilsolubility or polarity of the salt can be used.
- substituted amines are morpholine and ricinoleyl amine.
- Amines which form a preferred class of organic phosphate salts are those containing at least one substituent having at least 6 and preferably 6 to 30 carbon atoms. Examples of such amines are n-hexyl, n-docosyl, n-hexacosyl and n-triacontanyl amines, and aniline, toluidine, xylidine and lutidine. Amines within the preferred class that form especially effective organic phosphate salts for the purposes of this invention are primary and secondary amines having an aliphatic hydrocarbon substituent that contains a chain of from 6 to 18 carbon atoms.
- amines are cyclohexyl, nhexyl, dicyclohexyl, n-octyl, n-dodecyl, n-octadecyl and n-octadecenyl amines.
- Organic phosphates that form suitable amine salts for the purposes of this invention are diesters of phosphoric acids whose two ester substituents are hydrocarbon radicals containing 3 to 12 carbon atoms.
- Examples of such organic diesters of phosphoric acids are the dipropyl, diisoamyl, diisooctyl, didecyl, didodecyl, isoamyl, isooctyl, diphenyl, ditolyl, dicyclohexyl and dibenzyl esters of o-phosphoric acid.
- salts of organic phosphates Whose organic substituents are hydrocarbon radicals are preferred, salts of other organic phosphates whose organic substituents contain elements such as oxygen, chlorine, bromine, iodine, fluorine, nitrogen, sulfur and phosphorus which do not adversely aifect the oil-solubility or polarity of the ultimate amine salt can be used.
- organic phosphates examples include the diethylol, dipropylol, dipolyoxyethyleneethylol, dipolyoxypropylenepropylol ophosphates, and the diesters of dihydric and polyhydric alcohols such as ethylene glycol, sorbitol, mannitol, sorbitan, mannitan, pentaerythritol and o-phosphoric acid.
- amine salts within the preferred class of amine salts, the salts of organic phosphates whose two organic substituents are open-chain, saturated aliphatic hydrocarbon radicals containing from 3 to 12 carbon atoms are preferred.
- Such salts include, for example, amine salts of dipropyl, dibutyl, diisoamyl, di-n-octyl, diisooctyl, di-n-decyl, 3-methylbutyl, 2-ethylhexyl and didodecyl o-phosphates.
- preferred salts included by the scope of this invention are the oil-soluble amine salts of n-octyl, n-dodecyl (lauryl), n-octadecyl (stearyl), n-octadecenyl (oleyl), n-octadecadienyl (linoleyl), and cyclohexyl and dicyclohexyl amines, and di-n-propyl, di-nbutyl, diisoamyl, isoamyl isooctyl (3-methylbutyl, 2-ethylhexyl), di-n-octyl, diisooctyl, di-n-decyl and didodecyl o-phosphates.
- dioctyl o-phosphates those derived from the so-called oxo octyl alcohols, which, as is known, are highly branched-chain saturated aliphatic monohydric octyl alcohols prepared by the x0 process are particularly effective.
- the Oxo process briefly, involves the hydroformylation of olefinic hydrocarbons, followed by hydrogenation of the carbonylic compounds thus obtained.
- the olefinic hydrocarbons used in the manufacture of oxo-octyl alcohols are prepared by condensation of C and C olefins in the usual proportion in which they occur in petroleum refinery gases.
- oxo octyl alcohols normally will contain a mixture of branched-chain isomers of octyl alcohol, and the mix ture will consist mostly of isomeric dimethylhexanoles.
- the above-indicated composition is the most common for oxo-octyl alcohols, it will be appreciated that the proportions of the mixed isomeric alcohols can be varied to some extent by varying the proportions of the C and C olefins used in preparing the C olefin to be dehydroformylated.
- a specific example of a particularly effective agent for the purpose of the invention is the neutral addition salt (pH 7) of cocoamine and di oxo-octyl o-phosphoric acid.
- Other salts which can be used in accordance with the invention are the substantially neutral n-octyl amine, ndecyl amine, n-tetradecyl amine, n-hexadecyl and cyclohexyl amine salts of di oxo-octyl o-phosphoric acid.
- Suitable salts are the oil-soluble salts of n-hexyl, n-docosyl, n-docosenyl, n-triacontanyl and benzyl amines, toluidine, xylidine, lutidine, pyridine, piperidine, N-methyl aniline and N,N-dimethyl aniline and the diisoamyl and diisooctyl, dibenzyl, diphenyl and ditolyl esters of o-phosphoric acid.
- the amine salt of the diester of o-phosphoric acid is preferably used in an amount between about 0.01 and about 0.2 percent by weight based on the weight of the total composition. However, improved results can be obtained with an amount between about 0.001 and about 1.0 percent by weight without adversely affecting the other beneficial properties of the composition.
- the alkenyl-substituted succinic acid anhydride can be obtained by reacting an olefin, such as pentene, hexene, octylene, decene, dodecene, tetradecene, etc., or a mixture of such olefins, such as occurs in refinery gases, with maleic anhydride in accordance with known procedure which forms no part of this invention.
- the reaction is unique in that addition with maleic anhydride appears to take place at the alpha methylene carbon instead of the double bond.
- the reaction generally requires a temperature of 200 C. In the course of the reaction, resinous copolymers may also be formed.
- the alkenyl chain may contain from to 18 or even more carbon atoms.
- the acid anhydrides having an alkenyl group containing at least six carbon atoms are particularly advantageous.
- the especially preferred acid anhydrides are those in which the alkenyl substituent contains a relatively large number of carbon atoms, for example, 8 to 12 carbon atoms.
- dodecenyl succinic anhydride obtained from National Aniline Division, Allied Chemical Corporation.
- the alkenylsuccinic acid anhydride can be used in amounts of about 0.01 to about 0.3 percent by weight based on the weight of the total composition.
- the acid esters employed in accordance with this invention are the reaction products resulting from the esterification of a dimerized unsaturated fatty acid with a partial fatty acid ester of an alkitol anhydride.
- the ratio of reactants may range from one mol of dimerized acid per mol of partial fatty acid ester up to the number of mols of dimerized acid that is equal to the number of free hydroxyl groups in the partial fatty acid ester, per mol of partial fatty acid ester.
- the esterification reaction is eifected in conventional manner and under conventional conditions.
- the reaction is normally advantageously accelerated by heating the reactants, usually with refluxing and/or by the use of conventional esterification catalysts, such as hydrogen chloride, sulfuric acid, or an aromatic sulfonic acid, such as p-toluene-sulfonic acid.
- esterification catalysts such as hydrogen chloride, sulfuric acid, or an aromatic sulfonic acid, such as p-toluene-sulfonic acid.
- the reaction may be driven to substantial completion by removing one of the products of reaction. Since the herein disclosed dimeric unsaturated fatty acids, partial esters of alkitol anhydrides, and their reaction products boil at a temperature substantially above the boiling point of water, the reaction conveniently may be driven to completion by removal of the water of esterification by distillation. The removal of water from the reaction mixture may be facilitated by mechanical agitation, or by bubbling an inert gas, such as nitrogen, through the reaction mixture.
- one, two or three mols of dimerized acid may be esterified with one mol of a partial fatty acid ester containing three free hydroxyl groups, under conventional reaction conditions, with the elimination, respectively, of one, two or three mols of water of esterification, to form, respectively, a mono-, dior tri-acid or tricarboxylic ester of the dimerized acid and the partial fatty acid ester.
- reaction products may be prepared by effecting esterification of the reactants in mineral oil solution. This expedient is advantageous in that it prevents localized overheating of the reactants. Moreover, the resulting reaction products are in the form of mineral oil concentrates, the use of which often facilitates solution of the additives in their ultimate vehicles.
- the dimerized acids referred. to above are dimers, i.e., bimolecular addition products of conjugated or unconjugated dienoic or trienoic fatty acids having from 6 to 22 carbon atoms before dimerization.
- dimers i.e., bimolecular addition products of conjugated or unconjugated dienoic or trienoic fatty acids having from 6 to 22 carbon atoms before dimerization.
- Dimeric acids derived from dienoic and trienoic fatty acids are well known and can be prepared by conventional methods which form no part of this invention.
- dimerized acids capable of forming the compounds utilized in the composition of this invention are prepared from dienoic or trienoic fatty acids having the generic formula C H COOH, where n is an integer of from 5 to 21 and x is 3 or 5.
- such monomeric acids contain from 6 to 22 carbon atoms and may contain 2 or 3 ethylenic linkages as the ratio of carbon to hydrogen increases, i.e., as x increases from 3 to 5.
- Dimerized acids corresponding to the addition products of the foregoing acids therefore may be defined by the generic formula:
- n is an integer of from 10 to 42 and where x is an even integer of from 6 to 10.
- dimeric acids are therefore dibasic or dicarboxylic acids having from 12 to 44 carbon atoms.
- dimerized acids capable of forming the compounds employed in the compositions of this invention are dimers of dienoic acids such as sorbic (hexadienoic), linoleic (octadecadienoic), humoceric (nonadecadienoic) and eicosinic (eicosadienoic) acids.
- dimers of trienoic acids for example, linolenic and eleostearic (octadecatrienoic) acids also may be used.
- Dimers of mixed composition such as those obtained by dimerizing mixed dienoic, mixed trienoic or mixed dienoic and trienoic acids such as may be derived from certain naturally occurring drying oils, e.g., linseed oil and soybean oil, are quite satisfactory.
- Dienoic and trienoic acids having 18 carbon atoms, especially those having conjugated olefinic linkages, are preferred for reasons of economy of procurement, ease of reaction and the general excellence of the additives prepared therefrom.
- the partial esters of alkitol anhydrides and fatty acids adapted for use in the formation of the reaction products are those resulting from esterification with the desired fatty acid of at least one, but less than all, of the available hydroxyl groups of an alkitol anhydride.
- alkitol anhydride is meant an intramolecular, monoor di-anhydride of a polyhydric alcohol which contains at least 4 carbon atoms and at least 4 hydroxyl groups or mixtures of said anhydrides.
- alkitols Representative of the class of alkitols are erythritol; pentitols, such as arabitol, xylitol and adonitol; and hexitols such as mannitol, dulcitol and sorbitol, just as the xylitans and sorbitans are representative of the alkitol anhydrides, or alkitans.
- Fatty acids capable of forming partial esters of alkitol anhydrides suited to the preparation of the additives utilized in this invention are the fatty acids containing from 1.2 to 24 carbon atoms. These acids may be saturated or unsaturated, and they may be substituted with groups which do not adversely affect the oil-solubility or corrosion-inhibiting properties of the final reaction product. Representative of this group of acids are lauric acid, oleic acid, ricinoleic acid, stearic acid and lignostearic acid.
- Partial esters capable of reacting to form the reaction products include those formed by reacting a fatty acid of the foregoing kind with the desired alkitol anhydride in a molar ratio of at least 1:1 but less than that which would result in neutralization of all of the hydroxyl groups of the alkitol anhydride.
- the use of mixtures of partial fatty acid esters of alkitol anhydrides is also included within the scope of the invention.
- Specific examples of partial esters of alkitol anhydrides capable of reacting with dimeric unsaturated fatty acids to form acid esters which can be used in the composition of the invention are xylitan and sorbitan mono-, sesqui-, diand tri-oleates and stearates.
- Partial esters of hexitol anhydrides i.e., anhydrides of polyhydric alcohols containing 6 carbon atoms and 6 hydroxy groups, are preferred.
- acid esters of dimeric acids with partial fatty acid esters of alkitans which can be used in the compositions of this invention are the monoand poly-carboxylic acid esters of dimerized linoleic, linolenic and eleostearic acids with sorbitan and xylitan mono-, sesqui-, diand tri-oleates and stearates.
- Included within the foregoing representative class of compounds are mono-, di-, and triacid dilinoleic mono-, diand triesters of sorbitan monooleate, monoand diacid dilinoleic monoand di-esters of sorbitan dioleate, mono-acid dilinoleic mono-esters of sorbitan trioleate, monoand di-acid dilinoleic monoand diesters of xylitan monooleate, mono-acid dilinoleic mono-esters of xylitan dioleate and corresponding acid esters made from dimerized linolenic and eleostearic acids, as well as those made from partial esters of stearic acid.
- the amount of the acid ester employed in the composition of the invention depends upon the characteristic of the base oil as well as upon the amounts of other additive agents present. Satisfactory results can be obtained when the amount of acid ester comprises about 0.001 to about 1.0 percent by weight based on the weight of the total composition. A preferred range, however, comprises about 0.01 to about 0.2 percent by Weight.
- Caprylic acid which is used in the composition of the present invention is available commercially and, therefore, neither the compound per se nor its method of preparation constitutes any part of the present invention.
- the amount of caprylic acid which is used can vary over a narrow range depending upon the particular oil with which it is blended and upon the severity of the conditions to which the final lubricating composition is subjected. In general, the caprylic acid is employed in amounts of about 0.05 to about 0.2 percent by weight, based on the weight of the total lubricating composition.
- Morpholine which is used in the composition of the present invention is available commercially and, therefore, neither the compound per se nor its method of preparation constitutes any part of the present invention.
- the amount of morpholine which is used can vary over a small range and in general is based upon the amount of caprylic acid which is used. In general, we prefer to use an amount of morpholine which does not exceed the amount theoret ically required to convert all of the caprylic acid to morpholine caprylate. Effective vapor space inhibited turbine oils are obtained when using about 0.5 to about 1.0 times the theoretical amount of morpholine required to convert the caprylic acid to morpholine caprylate.
- morpholine While more than the stoichiometric amount of morpholine does not adversely affect the vapor space rust inhibiting characteristics of the lubricating composition, an excess of morpholine in combination with the other constituents in the lubricating composition of the invention adversely affects other characteristics of the lubricating composition such as its Water leachability. For this reason, we prefer a neutral or acidic mixture of caprylic acid and morpholine rather than a basic mixture of caprylic acid and morpholine. Thus, if 0.2 percent by Weight of caprylic acid is used in the lubricating composition, the morpholine should not exceed 0.12 percent by weight of the composition and preferably should comprise about 0.06 to about 0.12 percent by weight of the composition.
- the morpholine should not exceed 0.03 percent by weight of the composition and preferably should comprise about 0.015 to about 0.03 percent by Weight of the composition.
- An especially effective vapor space inhibited turbine oil composition contains about 0.1 percent by weight of caprylic acid and about 0.03 to about 0.06 percent by weight of morpholine.
- the caprylic acid and morpholine can be added separately in forming the composition of the invention, the caprylic acid and morpholine can, if desired, be reacted to form either an acidic mixture of morpholine caprylate and caprylic acid or a neutral morpholine caprylate salt.
- the acidic mixture or the neutral salt is then added to the lubricating composition.
- preparing the acidic mixture of morpholine caprylate and caprylic acid we employ from 0.5 to slightly less than 1.0 times the stoichiometric amount of morpholine required to neutralize the caprylic acid.
- the neutral morpholine caprylate salt We employ the stoichiometric amount of morpholine required to neutralize the caprylic acid.
- the acidic mixture of morpholine caprylate and caprylic acid or the neutral morpholine caprylate is employed in the lubricating composition, the acidic mixture or the neutral salt is used in amounts of about 0.05 to about 0.3 percent by weight based on the weight of the total lubricating composition.
- Especially effective vapor space inhibited turbine oil compositions contain about 0.1 to about 0.2 percent by weight of morpholine caprylate.
- the lubricating oil composition of this invention can contain other additive agents if desired to improve other specific properties without deleteriously affecting the beneficial properties of the composition.
- the oil can contain a pour point depressor, a viscosity and viscosity index improver, a dye, a sludge inhibitor and the like.
- a sulfurized monoester can be employed as an extreme pressure agent, if desired.
- the oil can contain a foam inhibitor such as oragno-silicon oxide condensation products, organo-silicol condensation products and the like.
- Exemplary of sulfurized monoesters useful as extreme pressure agents are the sulfurized monoester addition products of sulfur and an unsaturated ester of an aliphatic monohydric alcohol that contains 14 to 20 carbon atoms andnot more than one ethylenic linkage per molecule and an aliphatic monocarboxylic acid that contains to 20 carbon atoms and not more than one ethylenic linkage per molecule.
- the sulfurized monoesters useful in the present invention are well known materials and are characterized by a sulfur content of 6.0 to 16.0 percent.
- Examples of such materials are the fully sulfurized mono ester addition products of sulfur and unsaturated esters of normal decanoic, dodecanoic, dodecenoic, tetradecanoic, tetradecenoic, eicosanoic and eicosenoic acids and normal tetradecyl, tetradecenyl, hexadecyl, hexadecenyl, eicosyl and eicosenyl alcohols.
- Individual sulfurized monoesters of the class disclosed herein can be prepared conveniently by the method described in U.S. Pat. No. 2,179,065 to H. G. Smith.
- Mixed sulfurized monoesters useful for the purposes of this invention, such as sulfurized sperm oil can advantageously be prepared as described in US. Pat. No. 2,179,064 to H. G. Smith et al.
- Sperm oils sulfurized in accordance with the procedure described in US. Pat. No. 2,179,064 have a sulfur content in the range of 8 to 14 percent.
- the sulfurized monoesters are preferably present in an amount between about 0.01 and about 1.0 percent by weight based on the weight of the total composition. However, the preferred amount is between about 0.1 and about 0.3 percent by weight.
- the individual constituents of the composition of this invention can be added to the lubricating oil base in any order or simultaneously, either per se or in the form of mineral oil solutions.
- the latter practice is desirable in order to facilitate compounding of the compositions.
- some agitation of the compounded oil is desirable to facilitate forming a homogeneous composition, especially when the individual constituents are added in undiluted form to the base oil.
- cocoamine di-oxo-octyl orthophosphate and the dimerized linoleic acid-sorbitan monooleate acid ester employed in the compositions shown in Table I are obtained by procedures, shown in Examples I and II, respectively.
- the product of the foregoing reaction is a mineral oil concentrate of di oxo-octyl acid orthophosphate.
- di oxo-octyl acid orthophosphate-oil solution thus obtained are slowly added 210 g. (1 mol) of cocoamine (Armeen CD, Armour & Co.), with stirring, the temperature of the reaction being maintained below about 180 F. to avoid splitting out water from the mixture.
- cocoamine Armeen CD, Armour & Co.
- the mixture is brought to the desired pH of about 6.0 by the addition of suflicient cocoamine.
- the final mixture consisting principally of an oil solution of the ndodecyl amine salt of di oxo-octyl acid orthophosphate is then stirred for about 1 hour.
- EXAMPLE II (Dimerized linoleic acid-sorbitan monooleate acid ester) An acid ester of a dimeric unsaturated fatty acid and a partial fatty acid ester of an alkitol anhydride is prepared by admixture and reaction of 428 parts by weight of sorbitan monooleate (manufactured by the Atlas Powder Company of Wilmington, Del., and marketed under the name Span 80) with 560 parts by weight of dimerized linoleic acid (manufactured by Emery Industries, Inc. of Cincinnati, Ohio and marketed under the name of Empol 1022 Polymerized Fatty Acid). The reaction mixture is heated under reflux, until 18 parts by weight of water are trapped off, the maximum temperature reached by the reaction mixture being 500 F.
- the dimerized linoleic acid of this example has. the following typical characteristics:
- Typical properties of sorbitan monooleate are as folows:
- the product obtained in the above-described reaction is a clear, viscous liquid containing predominantly monoacid esters of dimerized linoleic acid and sorbitan monooleate, having the following typical physical properties:
- Neutralization value ASTM D974-51 T, total acid number 70. pH value, glass-calomel electrodes 4.6.
- compositions of the invention in comparison with compositions containing less than all of the constituents is demonstrated in a Vapor Space Rust Test which has been found to correlate with the condition encountered in the vapor space of a steam turbine.
- test oils are stirred by motor-driven stirrers which protrude through two holes in the chamber cover and two matching holes in the test box covers.
- the stirrers are metal, inch diameter with six blades, speed is 1750 rpm.
- the apparatus is disassembled and the steel and copper panels are dipped in a mixture of equal parts of hexane and acetone, air-dried and examined. The appearance of the copper panels are recorded.
- Each side of the four steel panels is rated as follows:
- a 1" x 3" freshly polished copper panel is mounted on the bottom surface of one of these top mounted panels.
- test boxes Two of these test boxes are inserted in a controlled temperature chamber.
- the water in the chamber is kept level with the level of the test oil.
- the water is automatically heated and cooled repeatedly by means of internal coils and is held at 175 F. for four hours, then maintained at 55 F. for four hours.
- the water bath is cooled from 175 to 55 F. over approximately minutes.
- the bath is heated from to 175 F. over approximately 45 minutes.
- the cooling time is considered part of the four hours at 55 F.; likewise, the heating period is part of the four hours at 175 F.
- the water is circulated from the chamber through coils soldered to the The satisfactory rust inhibiting properties for all compositions in contact with the metal according to Rust Test ASTM D665, Procedure A is evident from the data in Table I.
- composition D which con: tained neither caprylic acid nor morpholine and no morpholine caprylate failed the Procedure B test of ASTM D665.
- compositions of the invention Compositions B, C, E, F and G
- these compositions also provided excellent vapor space rust inhibition.
- the base oil compositions Compositions A and D
- which con tained neither caprylic acid nor morpholineand no morpholine caprylate gave very little protection in the Vapor Space Rust Test notwithstanding their ability to provide adequate protection in the ASTM D665, Procedure A evaluation.
- Cocoamine di-oxo-octyl orthopbosphate Oyclohexylamine salt of 3-rnethylbutyl,Z-ethylhexyl orthophosphat Cocoamine salt of 3-methylbutyl, 2-ethylhexyl ortl10ph0sphate n-Octylamino dfoxo-octyl orthophosphate Oxo-octylamine di-oxo-octyl orthophosphate.
- a lubricating composition comprising a major amount of a hydrocarbon lubricating oil and minor proportions consisting of about 0.1 to about 5.0 percent by weight of an alkyl phenol that contains at least one alkyl group containing 3 to 12 carbon atoms; about 0.001 to about 1.0 percent by weight of an amine salt of a diester of o-phosphoric acid; about 0.01 to about 0.3 percent by weight of an alkenyl-substituted succinic acid anhydride wherein the alkenyl group contains 5 to 18 carbon atoms; about 0.001 to about 1.0 percent by weight of an acid ester of (1) a dimeric acid derived from an unsaturated fatty acid containing 6 to 22 carbon atoms and having 2 to 3 ethylenic linkages per molecule and (2) a partial ester of a fattyacid containing 12 to 24 carbon atoms and an alkitolanhydride; about 0.05 to about 0.2 percent by weight of caprylic acid; and morpholine, said
- a lubricating composition comprising a. major amount of a hydrocarbon lubricating oil and minor proportions consisting of about 0.1 to about 5.0 percent by weight of an alkyl phenol, said alkenyl phenol containing at least one tertiary alkyl group containing between 3 and 12 carbon atoms; about 0.001 to about 1.0 percent by weight of an amine salt of a diester of o-phosphoric acid; about 0.01 to about 0.3 percent by weight of an alkenyl-substituted succinic acid anhydride wherein the alkenyl group contains 5 to 18 carbon atoms; about 0.001 to about 1.0 percent by weight of an acid ester of 1) a dimeric acid derived from an unsaturated fatty acid containing 6 to 22 carbon atoms and having 2 to 3 ethylenic linkages per molecule and (2) a partial ester of a fatty acid containing 12 to 24 carbon atoms and an alkitol anhydride; about 0.05 to about 0.2 percent by
- a lubricating composition comprising a major amount of a hydrocarbon lubricating oil and minor proportions consisting of about 0.1 to about 5.0 percent by weight of an alkyl phenol, said alkyl phenol containing at least one tertiary alkyl group containing between 3 and 12 carbon atoms; about 0.001 to about 1.0 percent by Weight of an amine salt of a dialkyl ester of o-phosphoric acid whose alkyl substituents each contain 3 to 12 carbon atoms; about 0.01 to about 0.3 percent by weight of an alkenyl-substituted succinic acid anhydride wherein the alkenyl group contains 5 to 18 carbon atoms; about 0.001 to about 1.0 percent by weight of an acid ester of (1) a dimeric acid derived from an unsaturated fatty acid containing 6 to 22 carbon atoms and having 2 to 3 ethylenic linkages per molecule and (2) a partial ester of a fatty acid containing 12 to 24 carbon atoms and
- a lubricating composition comprising a major amount of a hydrocarbon lubricating oil and minor proportions consisting of about 0.1 to about 5.0 percent by weight of any alkyl phenol, said' alkyl phenol containing at least one tertiary alkyl group containing between 3 and 12 carbon atoms; about 0.001 to about 1.0 percent by weight of an amine salt of a dialkyl ester of o-phosphoric acid whose alkyl substituent each.
- an alkenyl-substituted succinic acid anhydride wherein the alkenyl group contains 8 to 12 carbon atoms; about 0.001 to about 1.0 percent by weight of an acid ester of 1) a dimeric acid derived from an unsaturated fatty acid containing 6 to 22 carbon atoms and having 2 to 3 ethylenic linkages per molecule and (2) a partial ester of a fatty acid containing 12 to 24 carbon atoms and an alkitol anhydride; about 0.05 to about 0.2 percent by weight of caprylic acid; and morpholine, said morpholine comprising about 0.5 to about 1.0 times the theoretical amount required to convert the caprylic acid to morpholine caprylate.
- a lubricating composition comprising a major amount of a hydrocarbon lubricating oil and minor proportions consisting of about 0.1 to about 5.0 percent by weight of an alkyl phenol, said alkyl phenol containing at least one tertiary alkyl group containing between 3 and 12 carbon atoms; about 0.001 to about 1.0 percent by weight of an amine salt of a dialkyl ester of o-phosphoric acid whose alkyl substituents each contains 3 to 12 carbon atoms; about 0.01 to about 0.3 percent by weight of an alkenyl-substituted succinic acid anhydride wherein the alkenyl group contains 8 to 12 carbon atoms; about 0.001 to about 1.0 percent by weight of an acid ester of (1) a dimeric acid derived from an unsaturated fatty acid containing 18 carbon atoms and having from 2 to 3 ethylenic linkages per molecule and (2) a partial ester of a fatty acid containing 18 carbon atoms and a
- a lubricating composition comprising a major amount of a hydrocarbon lubricating oil and minor proportions consisting of about 0.1 to about 5.0 percent by weight of an alkyl phenol, said alkyl phenol containing at least one tertiary alkyl group containing between 3 and 12 carbon atoms; about 0.001 to about 1.0 percent by weight of an amine salt of a dialkyl ester of o-phosphoric acid whose alkyl substituents each contain 3 to 12 carbon atoms; about 0.01 to about 0.3 percent by weight of an alkenyl substituted succinic acid anhydride wherein the alkenyl group contains 8 to 12 carbon atoms; about 0.001 to about 1.0 percent by weight of an acid ester of 1) a dimeric acid derived from an unsaturated fatty acid containing 18 carbon atoms and having from 2 to 3 ethylenic linkages per molecule and (2) a partial ester of a fatty acid containing 18 carbon atoms and a hexito
- a lubricating composition comprising a major amount of a hydrocarbon lubricating oil; about 0.1 to about 5.0 percent by weight of 2,6-di-tertiary-butyl-4- methylphenol; about 0.001 to about 1.0 percent by weight of a salt of an aliphatic monoamine containing 6 to 18 carbon atoms and a dialkyl ester of o-phosphoric acid Whose alkyl substituents each contain 3 to 12 carbon atoms; about 0.01 to about 0.3 percent by weight of an alkenyl-substituted succinic acid anhydrate wherein the alkenyl group contains 8 to 12 carbon atoms; about 0.001 to about 1.0 percent by weight of an acid ester of a dimer of linoleic acid and sorbitan monooleate; about 0.05 to about 0.2 percent by weight of caprylic acid; and about 0.015 to about 0.12 percent by weight of morpholine, said morpholine comprising about 0.5 to about 1.0 times the
- a lubricating composition comprising a major amount of a hydrocarbon lubricating oil; about 0.1 to about 5.0 percent by weight of 2,6-di-tertiary-butyl-4- methylphenol; about 0.001 to about 1.0 percent by weight of the cocoamine salt of di-oxooctyl acid orthophosphate; about 0.01 to about 0.3 percent by weight of dodecenyl succinic anhydride; about 0.001 to about 1.0 percent by weight of an acid ester of a dimer of linoleic acid and sorbitan monooleate; and about 0.05 to about 0.3 percent by weight of morpholine caprylate.
- a lubricating composition comprising a major amount of a hydrocarbon lubricating oil; about 0.1 to about 5.0 percent by weight of 2,6-di-tertiary-buty1-4- methylphenol; about 0.001 to about 1.0 percent by weight of the cocoamine salt of di-oxo-octyl acid orthophosphate; about 0.01 to about 0.3 percent by weight of dodccenyl succinic anhydride; about 0.001 to about 1.0 percent by weight of an acid ester of a dimer of linoleic acid and sorbitan monooleate; about 0.05 to about 0.2 percent by Weight of caprylic acid; and about 0.015 to about 0.12 percent by weight of morpholine, said morpholine comprising about 0.5 to about 1.0 times the theoretical amount required to convert the caprylic acid to morpholine caprylate.
- a lubricating composition comprising a major amount of a hydrocarbon lubricating oil; about 0.1 to about 5.0 percent by weight of 2,6-di-tertiary-butyl-4- methylphenol; about 0.001 to about 1.0 percent by weight of the cocoamine salt of di-oXo-octyl acid orthophosphate; about 0.01 to about 0.3 percent by weight of dodecenyl succinic anhydride; about 0.001 to about 1.0 percent by weight of an acid ester of a dimer of linoleic acid and sorbitan monooleate; about 0.05 to about 0.2 percent by weight of caprylic acid; about 0.015 to about 0.12 percent by weight of morpholine, said morpholine comprising about 0.5 to about 1.0 times the theoretical amount required to convert the caprylic acid to morpholine caprylate; and about 0.01 to about 1.0 percent by weight of sulfurized sperm oil.
- R m N should read R N Column 6, lines 60 to 63 that portion of the "formula reading 11 2n--x H2n-x C should read Q OH H l 0 or; r 0
- R1 N should read R N Columnfi, lines 60 to 63 that portion of the formula reading n 2n-x H2n-x C should read C OH H H O OH 0 Column '7, line 53, after "inventiomfl' insert Accordingly,
- R N should read 6 R N
- Column 6, lines 60 to 63, that-portion of the formula reading n 2nX H2n i C I should read C OH H l H O OH I 0
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Abstract
A VAPOR SPACE INHIBITED TURBINE OIL COMPRISES (1) A MAJOR AMOUNT OF A MINERAL LUBRICATING OIL AND (2) A SMALL AMOUNT OF EACH OF (A) AN ALKYL PHENOL, E.G., 2,6-DI-TERTIARY-BUTYL-4-METHYLPHENOL; (B) AN AMINE SALT OF A DIESTER OF O-PHOSPHORIC ACID, E.G., COCOAMINE DI-OXO-OCTYL ORTHOPHOSPHATE; (C) AN ALKENYL-SUBSTITUTED SUCCINIC ACID ANHYDRIDE, E.G., DODECENYL SUCCINIC ANHYDRIDE; (D) AN ACID ESTER OF (1) A DIMERIC ACID DERIVED FROM AN UNSATURATED FATTY ACID AND (2) A PARTIAL ESTER OF A FATTY ACID AND AN ALKITOL ANHYDRIDE, E.G., DIMERIZED LINOLEIC ACID-SORBITAN MONOOLEATE ACID ESTER; (E) CAPRYLIC ACID; AND (F) MORPHOLINE, A SULFURIZED MONOESTER SUCH AS SULFURIZED SPERM OIL MAY ALSO BE EMPLOYED.
Description
United States Patent 3,785,975 VAPOR SPACE INHIBITED TURBINE OIL Earl L. Humphrey, Verona, and Willard B. Morse, New
Kensington, Pa., assignors to Gulf Research & Development Company, Pittsburgh, Pa. No Drawing. Filed June 18, 1971, Ser. No. 154,684 Int. Cl. Cm 1/48, N46 US. Cl. 252-325 10 Claims ABSTRACT OF THE DISCLOSURE A vapor space inhibited turbine oil comprises (1) a major amount of a mineral lubricating oil and (2) a small amount of each of (a) an alkyl phenol, e.g., 2,6-di-tertiary-butyl-4-methylphenol;
(b) an amine salt of a diester of o-phosphoric acid, e.g.,
cocoamine di-oXo-octyl orthophosphate;
(c) an alkenyl-substituted succinic acid anhydride, e.g.
dodecenyl succinic anhydride;
((1) an acid ester of (1) a dimeric acid derived from an unsaturated fatty acid and (2) a partial ester of a fatty acid and an alkitol anhydride, e.g., dimerized linoleic acid-sorbitan monooleate acid ester;
(e) caprylic acid; and
(f) morpholine.
A sulfurized monoester such as sulfurized sperm oil may also be employed.
This invention relates to lubricating oil compositions and more particularly to compounded turbine oils adapted to prevent rusting and/ or corrosion of metal parts in the vapor space of a steam turbine.
Various lubricating compositions have hereto-fore been disclosed for lubricating steam turbines but the prior compositions have not been entirely satisfactory. Some of the prior compositions have given good lubricating characteristics and/or have given protection against rusting and corrosion of metal turbine parts which are in contact with the lubricant but they have not given complete protection against rusting and/or corrosion of metal turbine parts not in intimate contact with the lubricant. It is desirable, therefore, to provide a lubricating composition which not only will protect metal surfaces in contact with the lubricant from rusting but also will protect metal surfaces in the vapor space above said lubricant from rusting.
Compositions having good lubricating characteristics and/ or good antirust and anticorrosion characteristics have been disclosed in US. Pats. Nos. 2,767,144 to R. I. Gottshall et al.; 2,786,028 to R. I. Gottshall et al.; 2,789,- 950 to R. I. Gottshall et al.; 2,789,951 to R. T. Kern et al. and 2,789,952 to T. L. Cantrell et al. The make-up of the lubricating compositions disclosed in the aforesaid patents are briefly set forth in the following paragraphs.
US. Pat. No. 2,767,144 to R. I. Gottshall et al. dis closes a lubricating composition consisting essentially of a major amount of a lubricating oil and a minor amount of an acid ester of (l) a dimeric acid derived from an unsaturated fatty acid containing from 6 to 22 carbon atoms and having from 2 to 3 ethylenic linkages per molecule and (2) a partial ester of a fatty acid containing from 12 to 24 carbon atoms and an alkitol anhydride.
US. Pat. No. 2,789,952 to T. L. Cantrellet al. discloses a lubricating composition consisting essentially .of
3,785,975 Patented Jan. l5, 1 974 ice a major amount of a lubricating; oil and minor amounts of each of a metal alkyl thiophosphate, an alkyl phenol and a substantially neutral addition product of isoamyl octyl acid phosphate with primary fatty amines containing from 8 to 18 carbon atoms.
US. Pat. No. 2,789,950 to R. I. Gottshall et al. discloses a lubricating composition consisting essentially of a major amount of a lubricating oil and minor amounts of each of an alkyl phenol, a substantially neutral addi tion product of isoamyl octyl acid phosphate with primary fatty amines containing from 8 to 18 carbon atoms, and an acid ester of (1) a dimeric acid derived from an unsaturated fatty acid containing from 6 to 22 carbon atoms and having from 2 to 3 ethylenic linkages per molecule and (2) a partial ester of a fatty acid containing from 12 to 24 carbon atoms and an alkitol anhydride.
US. Pat. No. 2,789,951 to R. T. Kern et a1. discloses a lubricating composition consisting essentially of a major amount of a lubricating oil and minor amounts of each of a metal alkyl thiophosphate, an alkyl phenol, a substantially neutral addition product of isoamyl octyl acid phosphate with primary fatty amines containing from 8 to 18 carbon atoms, and an acid ester of (l) a dimeric acid derived from an unsaturated fatty acid containing from 6 to 22 carbon atoms and having from 2 to 3 ethylenic linkages per molecule and (2) a partial ester of a fatty acid containing from 12 to 24 carbon atoms and an alkitol anhydride.
US. Pat. No. 2,786,028 to R. I. Gottshall et al. disclosesa lubricating composition consisting essentially of a major amount of a lubricating oil and minor amounts of :each of an alkyl phenol, a substantially neutral addition product of isoamyl octyl acid phosphate with a primary fatty amine containing from 8 to l8 carbon atoms, an alkenyl-substituted succinic acid anhydride wherein the alkenyl group contains from 5 to 18 carbon atoms, and an acid ester of (l) a dimeric acid derived from an un saturated fatty acid containing from 6 to 22 carbon atoms and having from 2 to 3 ethylenic linkages per molecule and (2) a partial ester of a fatty acid containing from 12 to 24 carbon atoms and an alkitol anhydride. 7 1
While the lubricating compositions disclosed in the above patents, in general, have good lubricating charac' teristics combined with good oxidation stability and good rust-inhibiting properties so long as the lubricating com positions are in contact with the surfaceto be lubricated, the compositions do not possess the characteristics of lubricating compositions adapted to prevent rusting and/or corrosion of metal parts in the vapor space of asteam turbine. v t
We have found that a composition having good lubricating characteristics combined with antirust and anti corrosion properties both to metal surface in contact with the composition andto metal surfaces not in intimate contact with the composition, such as metal sur-. faces in the vapor space of a steam turbine, can be 0b-' tained by incorporating in a major amount of a mineral lubricating oil a small amount of each of (a) an alkyl phenol; (b) an amine salt' of a diester of (J-phosphoric acid; (c) an alkenyl-sub'stituted succinic acid anhydride wherein the alkenyl group contains 5 to 18 carbon atornsf (d) an acid ester of (l) a dimeric acid derived from an unsaturated fatty acid containing 6 to 22 carbon atoms and having 2 to 3 ethylenic linkages per molecule and i (2) a partial ester of a fatty acid containing 12 to 24 car- 3 bon atoms and an alkitol anhydride; (e) caprylic acid; and (f) morpholine. Thus, the lubricating composition of our invention comprises a major amount of a mineral lubricating oil and a small amount of each of the constituents designated hereinabove as (a), (b), (c), (d), (e) and (f).
The mineral lubricating oil to which the other constitucuts are added is advantageously a refined or semirefined parafl'inic base oil. A mineral oil which has been treated with hydrogen, because of its improved stability over the untreated oil, is particularly suitable as a lubricating oil base for preparing a lubricant to be used in a steam turbine. For this reason, a preferred embodiment of the invention utilizes a mineral lubricating oil which has been treated with hydrogen whereby extensive hydrogenation of the olefinic and/or aromatic constituents present in the charge stock has been efiected. The hydrogen treating process may be either a hydrofinishing process or a hydrotreating process. The method by which a hydrogenated mineral lubricating oil is obtained is not a part of the present invention. The viscosity requirements of the mineral oil employed in preparing a composition of the invention will vary depending upon the end use of the lubricant. Thus, various grades of oil extending from light to extra heavy oils can be employed. Oils within this range may have viscosities of about 100 to about 2500 SUS at 100 F. If desired, a blend of oils of suitable viscosity may be employed instead of a single oil by means of which any desired viscosity may be secured. The mineral oil content of the composition of the invention comprises about 90 to about 99.5 percent by weight of the total composition. The particular mineral lubricating oil a well as the exact amount of such oil employed, therefore, depends upon the characteristics desired in the final composition.
The alkyl phenol which is used in accordance with the invention is advantageously a dior tri-alkylated phenol or cresol with at least one of the alkyl groups being a tertiary alkyl group. The alkyl groups are preferably those containing between 3 and 12 carbon atoms. Good results can be obtained with a tri-tertiary butyl phenol or a ditertiary butyl cresol. Examples of the preferred alkylated phenols are 2,4,6-tri-tertiary-butylphenol and 2,6-di-tertiary-butyl-4-methylphenol. The alkyl phenols can be used in amounts of about 0.1 to about 5.0 percent by weight based on the weight of the total composition. The preferred amount, however, is between about 0.2 and about 1.25 percent by weight.
The amine salt of the diester of o-phosphoric acid is conveniently prepared by neutralizing a diester of the particular phosphoric acid with approximately stoichiometric proportions of an amine of the class described herein. In most instances, it is advantageous that the pH of the reaction mixture be adjusted to substantially neutral, i.e., between about 5.5 and about 7.5, by controlling the amount of amine introduced into the reaction. In the case of amines that are very weak bases, however, a lower pH, for example, of the order of 3.0 or 3.5 is satisfactory. The neutralization reaction normally takes place spontaneously or substantially so, with the evolution of heat. It is preferable to maintain the reaction temperature below about 180 F., cooling the reaction mixture if necessary. In no case should the temperature of the reaction mixture be allowed to rise above about 200 P. if appreciable decomposition of the resulting salt is to be avoided. The preparation of typical salts, the use of which is included by this invention, is set forth in detail in U.S. Pat. No. 2,387,537 to H. G. Smith et a1.
Amines which form suitable amine salts ofr the purposes of this invention are those having the general formula:
where R, R and R are hydrogen or organic radicals. Thus, suitable salts for the purpose of this invention are formed by primary, secondary and tertiary amines whose organic substituents can be either aliphatic radicals, including saturated, unsaturated, cyclic, branched chain and straight chain radicals or aromatic radicals.
Thus, for example, the invention includes the use of oilsoluble organic phosphate salts of primary, secondary and tertiary, straight or branched chain alkyl, alkenyl and alkadienyl amines, and primary, secondary, and tertiary cycloalkyl amines, heterocyclic amines, and primary, secondary and tertiary aryl amines, including alkaryl and aralkyl amines. Representative examples of such amines are butyl, tributyl, octyl, dioctyl, dodecyl, octadecyl, octadecadienyl, cyclopentyl, cyclohexyl, dicyclohexyl, cycloheptyl and abietyl (rosin) amines, aniline, N-methyl aniline, N,N-dimethyl aniline, toluidine, xylidine, pyridine, piperidine and the like. Commercial mixtures of amines, such as cocoamine, form highly satisfactory phosphate salts of the kind included by the invention. Cocoamine is a mixture of amines prepared from coconut oil fatty acids and contains a predominant amount of n-dodecyl amine (lauryl amine), together with minor amounts of n-octyl, n-decyl, n-tetradecyl, n-hexadecyl, n-octadecyl and n-octadecenyl amines. Another suitable commercial amine mixture is tallow amine, a mixture of C n-alkyl and alkenyl amines derived from animal tallow fatty acids. Although salts of amines containing hydrocarbon substituents are preferred, salts of amines whose substituents contain elements such as oxygen, halogens, sulfur, nitrogen or phosphoru which do not adversely affect the oilsolubility or polarity of the salt can be used. Examples of such substituted amines are morpholine and ricinoleyl amine.
Amines which form a preferred class of organic phosphate salts are those containing at least one substituent having at least 6 and preferably 6 to 30 carbon atoms. Examples of such amines are n-hexyl, n-docosyl, n-hexacosyl and n-triacontanyl amines, and aniline, toluidine, xylidine and lutidine. Amines within the preferred class that form especially effective organic phosphate salts for the purposes of this invention are primary and secondary amines having an aliphatic hydrocarbon substituent that contains a chain of from 6 to 18 carbon atoms. Representative examples of such amines are cyclohexyl, nhexyl, dicyclohexyl, n-octyl, n-dodecyl, n-octadecyl and n-octadecenyl amines.
Organic phosphates that form suitable amine salts for the purposes of this invention are diesters of phosphoric acids whose two ester substituents are hydrocarbon radicals containing 3 to 12 carbon atoms. Examples of such organic diesters of phosphoric acids are the dipropyl, diisoamyl, diisooctyl, didecyl, didodecyl, isoamyl, isooctyl, diphenyl, ditolyl, dicyclohexyl and dibenzyl esters of o-phosphoric acid. Although salts of organic phosphates Whose organic substituents are hydrocarbon radicals are preferred, salts of other organic phosphates whose organic substituents contain elements such as oxygen, chlorine, bromine, iodine, fluorine, nitrogen, sulfur and phosphorus which do not adversely aifect the oil-solubility or polarity of the ultimate amine salt can be used. Examples of such organic phosphates are the diethylol, dipropylol, dipolyoxyethyleneethylol, dipolyoxypropylenepropylol ophosphates, and the diesters of dihydric and polyhydric alcohols such as ethylene glycol, sorbitol, mannitol, sorbitan, mannitan, pentaerythritol and o-phosphoric acid.
Within the preferred class of amine salts, the salts of organic phosphates whose two organic substituents are open-chain, saturated aliphatic hydrocarbon radicals containing from 3 to 12 carbon atoms are preferred. Such salts include, for example, amine salts of dipropyl, dibutyl, diisoamyl, di-n-octyl, diisooctyl, di-n-decyl, 3-methylbutyl, 2-ethylhexyl and didodecyl o-phosphates.
Specific examples of preferred salts included by the scope of this invention are the oil-soluble amine salts of n-octyl, n-dodecyl (lauryl), n-octadecyl (stearyl), n-octadecenyl (oleyl), n-octadecadienyl (linoleyl), and cyclohexyl and dicyclohexyl amines, and di-n-propyl, di-nbutyl, diisoamyl, isoamyl isooctyl (3-methylbutyl, 2-ethylhexyl), di-n-octyl, diisooctyl, di-n-decyl and didodecyl o-phosphates.
Of the dioctyl o-phosphates, those derived from the so-called oxo octyl alcohols, which, as is known, are highly branched-chain saturated aliphatic monohydric octyl alcohols prepared by the x0 process are particularly effective. The Oxo process, briefly, involves the hydroformylation of olefinic hydrocarbons, followed by hydrogenation of the carbonylic compounds thus obtained. Normally, the olefinic hydrocarbons used in the manufacture of oxo-octyl alcohols are prepared by condensation of C and C olefins in the usual proportion in which they occur in petroleum refinery gases. In this case, oxo octyl alcohols normally will contain a mixture of branched-chain isomers of octyl alcohol, and the mix ture will consist mostly of isomeric dimethylhexanoles. Although the above-indicated composition is the most common for oxo-octyl alcohols, it will be appreciated that the proportions of the mixed isomeric alcohols can be varied to some extent by varying the proportions of the C and C olefins used in preparing the C olefin to be dehydroformylated.
A specific example of a particularly effective agent for the purpose of the invention is the neutral addition salt (pH 7) of cocoamine and di oxo-octyl o-phosphoric acid. Other salts which can be used in accordance with the invention are the substantially neutral n-octyl amine, ndecyl amine, n-tetradecyl amine, n-hexadecyl and cyclohexyl amine salts of di oxo-octyl o-phosphoric acid.
Other examples of suitable salts are the oil-soluble salts of n-hexyl, n-docosyl, n-docosenyl, n-triacontanyl and benzyl amines, toluidine, xylidine, lutidine, pyridine, piperidine, N-methyl aniline and N,N-dimethyl aniline and the diisoamyl and diisooctyl, dibenzyl, diphenyl and ditolyl esters of o-phosphoric acid.
The amine salt of the diester of o-phosphoric acid is preferably used in an amount between about 0.01 and about 0.2 percent by weight based on the weight of the total composition. However, improved results can be obtained with an amount between about 0.001 and about 1.0 percent by weight without adversely affecting the other beneficial properties of the composition.
The alkenyl-substituted succinic acid anhydride can be obtained by reacting an olefin, such as pentene, hexene, octylene, decene, dodecene, tetradecene, etc., or a mixture of such olefins, such as occurs in refinery gases, with maleic anhydride in accordance with known procedure which forms no part of this invention. The reaction is unique in that addition with maleic anhydride appears to take place at the alpha methylene carbon instead of the double bond. The reaction generally requires a temperature of 200 C. In the course of the reaction, resinous copolymers may also be formed. The alkenyl chain may contain from to 18 or even more carbon atoms. The acid anhydrides having an alkenyl group containing at least six carbon atoms are particularly advantageous. The especially preferred acid anhydrides are those in which the alkenyl substituent contains a relatively large number of carbon atoms, for example, 8 to 12 carbon atoms. In illustrating the composition of the invention, we have used a commercially available material, dodecenyl succinic anhydride, obtained from National Aniline Division, Allied Chemical Corporation. The alkenylsuccinic acid anhydride can be used in amounts of about 0.01 to about 0.3 percent by weight based on the weight of the total composition.
The acid esters employed in accordance with this invention are the reaction products resulting from the esterification of a dimerized unsaturated fatty acid with a partial fatty acid ester of an alkitol anhydride. The ratio of reactants may range from one mol of dimerized acid per mol of partial fatty acid ester up to the number of mols of dimerized acid that is equal to the number of free hydroxyl groups in the partial fatty acid ester, per mol of partial fatty acid ester.
The esterification reaction is eifected in conventional manner and under conventional conditions. Thus, while esterification may proceed slowly at room temperature, the reaction is normally advantageously accelerated by heating the reactants, usually with refluxing and/or by the use of conventional esterification catalysts, such as hydrogen chloride, sulfuric acid, or an aromatic sulfonic acid, such as p-toluene-sulfonic acid. The reaction may be driven to substantial completion by removing one of the products of reaction. Since the herein disclosed dimeric unsaturated fatty acids, partial esters of alkitol anhydrides, and their reaction products boil at a temperature substantially above the boiling point of water, the reaction conveniently may be driven to completion by removal of the water of esterification by distillation. The removal of water from the reaction mixture may be facilitated by mechanical agitation, or by bubbling an inert gas, such as nitrogen, through the reaction mixture.
By way of illustrating the foregoing process, one, two or three mols of dimerized acid may be esterified with one mol of a partial fatty acid ester containing three free hydroxyl groups, under conventional reaction conditions, with the elimination, respectively, of one, two or three mols of water of esterification, to form, respectively, a mono-, dior tri-acid or tricarboxylic ester of the dimerized acid and the partial fatty acid ester.
If desired, the reaction products may be prepared by effecting esterification of the reactants in mineral oil solution. This expedient is advantageous in that it prevents localized overheating of the reactants. Moreover, the resulting reaction products are in the form of mineral oil concentrates, the use of which often facilitates solution of the additives in their ultimate vehicles.
The dimerized acids referred. to above are dimers, i.e., bimolecular addition products of conjugated or unconjugated dienoic or trienoic fatty acids having from 6 to 22 carbon atoms before dimerization. Dimeric acids derived from dienoic and trienoic fatty acids are well known and can be prepared by conventional methods which form no part of this invention.
More particularly, dimerized acids capable of forming the compounds utilized in the composition of this invention are prepared from dienoic or trienoic fatty acids having the generic formula C H COOH, where n is an integer of from 5 to 21 and x is 3 or 5. As will be evident, such monomeric acids contain from 6 to 22 carbon atoms and may contain 2 or 3 ethylenic linkages as the ratio of carbon to hydrogen increases, i.e., as x increases from 3 to 5. Dimerized acids corresponding to the addition products of the foregoing acids therefore may be defined by the generic formula:
where n is an integer of from 10 to 42 and where x is an even integer of from 6 to 10. These dimeric acids are therefore dibasic or dicarboxylic acids having from 12 to 44 carbon atoms.
Representative members of the class of dimerized acids capable of forming the compounds employed in the compositions of this invention are dimers of dienoic acids such as sorbic (hexadienoic), linoleic (octadecadienoic), humoceric (nonadecadienoic) and eicosinic (eicosadienoic) acids. Dimers of trienoic acids, for example, linolenic and eleostearic (octadecatrienoic) acids also may be used.
It is not necessary that both of the unsaturated fatty acid molecules of the bimolecular addition product be identical. Dimers of mixed composition such as those obtained by dimerizing mixed dienoic, mixed trienoic or mixed dienoic and trienoic acids such as may be derived from certain naturally occurring drying oils, e.g., linseed oil and soybean oil, are quite satisfactory.
Dienoic and trienoic acids having 18 carbon atoms, especially those having conjugated olefinic linkages, are preferred for reasons of economy of procurement, ease of reaction and the general excellence of the additives prepared therefrom.
The partial esters of alkitol anhydrides and fatty acids adapted for use in the formation of the reaction products are those resulting from esterification with the desired fatty acid of at least one, but less than all, of the available hydroxyl groups of an alkitol anhydride. By alkitol anhydride is meant an intramolecular, monoor di-anhydride of a polyhydric alcohol which contains at least 4 carbon atoms and at least 4 hydroxyl groups or mixtures of said anhydrides. Representative of the class of alkitols are erythritol; pentitols, such as arabitol, xylitol and adonitol; and hexitols such as mannitol, dulcitol and sorbitol, just as the xylitans and sorbitans are representative of the alkitol anhydrides, or alkitans.
Fatty acids capable of forming partial esters of alkitol anhydrides suited to the preparation of the additives utilized in this invention are the fatty acids containing from 1.2 to 24 carbon atoms. These acids may be saturated or unsaturated, and they may be substituted with groups which do not adversely affect the oil-solubility or corrosion-inhibiting properties of the final reaction product. Representative of this group of acids are lauric acid, oleic acid, ricinoleic acid, stearic acid and lignostearic acid.
Partial esters capable of reacting to form the reaction products include those formed by reacting a fatty acid of the foregoing kind with the desired alkitol anhydride in a molar ratio of at least 1:1 but less than that which would result in neutralization of all of the hydroxyl groups of the alkitol anhydride. The use of mixtures of partial fatty acid esters of alkitol anhydrides is also included Within the scope of the invention. Specific examples of partial esters of alkitol anhydrides capable of reacting with dimeric unsaturated fatty acids to form acid esters which can be used in the composition of the invention are xylitan and sorbitan mono-, sesqui-, diand tri-oleates and stearates. Partial esters of hexitol anhydrides, i.e., anhydrides of polyhydric alcohols containing 6 carbon atoms and 6 hydroxy groups, are preferred.
The partial esters of alkitol anhydrides disclosed herein as well as the method of preparing the same are conventional and form no part of the present invention.
Representative specific examples of acid esters of dimeric acids with partial fatty acid esters of alkitans which can be used in the compositions of this invention are the monoand poly-carboxylic acid esters of dimerized linoleic, linolenic and eleostearic acids with sorbitan and xylitan mono-, sesqui-, diand tri-oleates and stearates. Included within the foregoing representative class of compounds are mono-, di-, and triacid dilinoleic mono-, diand triesters of sorbitan monooleate, monoand diacid dilinoleic monoand di-esters of sorbitan dioleate, mono-acid dilinoleic mono-esters of sorbitan trioleate, monoand di-acid dilinoleic monoand diesters of xylitan monooleate, mono-acid dilinoleic mono-esters of xylitan dioleate and corresponding acid esters made from dimerized linolenic and eleostearic acids, as well as those made from partial esters of stearic acid.
The amount of the acid ester employed in the composition of the invention depends upon the characteristic of the base oil as well as upon the amounts of other additive agents present. Satisfactory results can be obtained when the amount of acid ester comprises about 0.001 to about 1.0 percent by weight based on the weight of the total composition. A preferred range, however, comprises about 0.01 to about 0.2 percent by Weight.
Caprylic acid which is used in the composition of the present invention is available commercially and, therefore, neither the compound per se nor its method of preparation constitutes any part of the present invention. The amount of caprylic acid which is used can vary over a narrow range depending upon the particular oil with which it is blended and upon the severity of the conditions to which the final lubricating composition is subjected. In general, the caprylic acid is employed in amounts of about 0.05 to about 0.2 percent by weight, based on the weight of the total lubricating composition.
Morpholine which is used in the composition of the present invention is available commercially and, therefore, neither the compound per se nor its method of preparation constitutes any part of the present invention. The amount of morpholine which is used can vary over a small range and in general is based upon the amount of caprylic acid which is used. In general, we prefer to use an amount of morpholine which does not exceed the amount theoret ically required to convert all of the caprylic acid to morpholine caprylate. Effective vapor space inhibited turbine oils are obtained when using about 0.5 to about 1.0 times the theoretical amount of morpholine required to convert the caprylic acid to morpholine caprylate. While more than the stoichiometric amount of morpholine does not adversely affect the vapor space rust inhibiting characteristics of the lubricating composition, an excess of morpholine in combination with the other constituents in the lubricating composition of the invention adversely affects other characteristics of the lubricating composition such as its Water leachability. For this reason, we prefer a neutral or acidic mixture of caprylic acid and morpholine rather than a basic mixture of caprylic acid and morpholine. Thus, if 0.2 percent by Weight of caprylic acid is used in the lubricating composition, the morpholine should not exceed 0.12 percent by weight of the composition and preferably should comprise about 0.06 to about 0.12 percent by weight of the composition. If 0.05 percent by Weight of caprylic acid is used in the lubricating composition, the morpholine should not exceed 0.03 percent by weight of the composition and preferably should comprise about 0.015 to about 0.03 percent by Weight of the composition. An especially effective vapor space inhibited turbine oil composition contains about 0.1 percent by weight of caprylic acid and about 0.03 to about 0.06 percent by weight of morpholine.
While the caprylic acid and morpholine can be added separately in forming the composition of the invention, the caprylic acid and morpholine can, if desired, be reacted to form either an acidic mixture of morpholine caprylate and caprylic acid or a neutral morpholine caprylate salt. The acidic mixture or the neutral salt is then added to the lubricating composition. In preparing the acidic mixture of morpholine caprylate and caprylic acid we employ from 0.5 to slightly less than 1.0 times the stoichiometric amount of morpholine required to neutralize the caprylic acid. In preparing the neutral morpholine caprylate salt, We employ the stoichiometric amount of morpholine required to neutralize the caprylic acid. If either the acidic mixture of morpholine caprylate and caprylic acid or the neutral morpholine caprylate is employed in the lubricating composition, the acidic mixture or the neutral salt is used in amounts of about 0.05 to about 0.3 percent by weight based on the weight of the total lubricating composition. Especially effective vapor space inhibited turbine oil compositions contain about 0.1 to about 0.2 percent by weight of morpholine caprylate.
The lubricating oil composition of this invention can contain other additive agents if desired to improve other specific properties without deleteriously affecting the beneficial properties of the composition. For example, the oil can contain a pour point depressor, a viscosity and viscosity index improver, a dye, a sludge inhibitor and the like. A sulfurized monoester can be employed as an extreme pressure agent, if desired. Also, if desired, the oil can contain a foam inhibitor such as oragno-silicon oxide condensation products, organo-silicol condensation products and the like.
Exemplary of sulfurized monoesters useful as extreme pressure agents are the sulfurized monoester addition products of sulfur and an unsaturated ester of an aliphatic monohydric alcohol that contains 14 to 20 carbon atoms andnot more than one ethylenic linkage per molecule and an aliphatic monocarboxylic acid that contains to 20 carbon atoms and not more than one ethylenic linkage per molecule. The sulfurized monoesters useful in the present invention are well known materials and are characterized by a sulfur content of 6.0 to 16.0 percent. Examples of such materials are the fully sulfurized mono ester addition products of sulfur and unsaturated esters of normal decanoic, dodecanoic, dodecenoic, tetradecanoic, tetradecenoic, eicosanoic and eicosenoic acids and normal tetradecyl, tetradecenyl, hexadecyl, hexadecenyl, eicosyl and eicosenyl alcohols. Individual sulfurized monoesters of the class disclosed herein can be prepared conveniently by the method described in U.S. Pat. No. 2,179,065 to H. G. Smith. Mixed sulfurized monoesters useful for the purposes of this invention, such as sulfurized sperm oil, can advantageously be prepared as described in US. Pat. No. 2,179,064 to H. G. Smith et al.
Sperm oils sulfurized in accordance with the procedure described in US. Pat. No. 2,179,064 have a sulfur content in the range of 8 to 14 percent. When used, the sulfurized monoesters are preferably present in an amount between about 0.01 and about 1.0 percent by weight based on the weight of the total composition. However, the preferred amount is between about 0.1 and about 0.3 percent by weight.
The individual constituents of the composition of this invention can be added to the lubricating oil base in any order or simultaneously, either per se or in the form of mineral oil solutions. The latter practice is desirable in order to facilitate compounding of the compositions. After addition of the individual constituents to the base oil, some agitation of the compounded oil is desirable to facilitate forming a homogeneous composition, especially when the individual constituents are added in undiluted form to the base oil.
The cocoamine di-oxo-octyl orthophosphate and the dimerized linoleic acid-sorbitan monooleate acid ester employed in the compositions shown in Table I are obtained by procedures, shown in Examples I and II, respectively.
. EXAMPLE .1
.. ,...(Cocoamine. di-oxoroctyl.orthophosphate) Specific gravity, 20/20 C. -2 0.8324
Viscosity, kinematic, cs., 20 C 12.43 Refractive index, m 1.4313- C alcohol content, percent by wt. 99.3 C carbonyl content, percent by wt 0.06 Distillation, isooctyl, alcohol, ASTM D1078-49 Over point 1840 Dry point 188.5 10% 185.5
The product of the foregoing reaction is a mineral oil concentrate of di oxo-octyl acid orthophosphate. To 441 g. (1 mol) of the di oxo-octyl acid orthophosphate-oil solution thus obtained are slowly added 210 g. (1 mol) of cocoamine (Armeen CD, Armour & Co.), with stirring, the temperature of the reaction being maintained below about 180 F. to avoid splitting out water from the mixture. The mixture is brought to the desired pH of about 6.0 by the addition of suflicient cocoamine. The final mixture consisting principally of an oil solution of the ndodecyl amine salt of di oxo-octyl acid orthophosphate is then stirred for about 1 hour.
EXAMPLE II (Dimerized linoleic acid-sorbitan monooleate acid ester) An acid ester of a dimeric unsaturated fatty acid and a partial fatty acid ester of an alkitol anhydride is prepared by admixture and reaction of 428 parts by weight of sorbitan monooleate (manufactured by the Atlas Powder Company of Wilmington, Del., and marketed under the name Span 80) with 560 parts by weight of dimerized linoleic acid (manufactured by Emery Industries, Inc. of Cincinnati, Ohio and marketed under the name of Empol 1022 Polymerized Fatty Acid). The reaction mixture is heated under reflux, until 18 parts by weight of water are trapped off, the maximum temperature reached by the reaction mixture being 500 F. The dimerized linoleic acid of this example has. the following typical characteristics:
Physical state Bright liquid. Molecular weight 564 (approx.). Gravity: API 16.4. Viscosity, SUV, 210 F. 335. Flash, 00: F. 530. Fire, 0C: F. 600.
Color, ASTM Union 3.25. Saponification No. 194. Neutralization No 195. Dimer content -2 85% (approx.). Trimer and higher 12% (approx.). Monomer 3% (approx.).
1 Typical properties of sorbitan monooleate are as folows:
Molecular weight 428 (approx.).
Gravity: API 10.1. SP. gr., 60/60 F. 0.999. Lb./gal., 60 F. 8.32. Viscosity, SUV, sec.:
F 1827. 210 F. 108.3. Flash, P-M: F 410. Flash, 0C: F. 450. Fire, 0C: F. 545. Pourr F. +10. Physical state, room temp. Viscous liquid. Color, ASTM D 3.0. Water, percent 0.3. Carbon residue, Conradson, percent 2.94. Acid ,No. 6.5. pH value. 7.0. Saponification Number 155. Hydroxyl Number 203. Ash, percent 0.116.
The product obtained in the above-described reaction is a clear, viscous liquid containing predominantly monoacid esters of dimerized linoleic acid and sorbitan monooleate, having the following typical physical properties:
Neutralization value, ASTM D974-51 T, total acid number 70. pH value, glass-calomel electrodes 4.6.
The efiectivenes of compositions of the invention in comparison with compositions containing less than all of the constituents is demonstrated in a Vapor Space Rust Test which has been found to correlate with the condition encountered in the vapor space of a steam turbine. In
accordance with this test, approximately 1800 ml. of the 2 test oil are poured into a stainless steel box eight inches on each side. Two 2" x 6" x A sandblasted steel panels are suspended vertically on opposite sides of the box above the oil level. Two similar sandblasted steel panels covers of the test boxes and back to the bath. The circulation rate is approximately /2 gaL/min. through each coil. The test oils are stirred by motor-driven stirrers which protrude through two holes in the chamber cover and two matching holes in the test box covers. The stirrers are metal, inch diameter with six blades, speed is 1750 rpm.
At the end of the 72-hour test period (which may be 24 hours for screening tests), the apparatus is disassembled and the steel and copper panels are dipped in a mixture of equal parts of hexane and acetone, air-dried and examined. The appearance of the copper panels are recorded.
Each side of the four steel panels is rated as follows:
5=c1ean to a few small spots of rust.
4=light rust, many small spots or several large spots of rust.
3=medium rust, numerous spots of rust.
2=heavy rust, continuous areas of rust.
1 all rust or large areas of rust.
The rust ratingshown is the sum of values for the eight panel areas; i.e., 40=perfect, 8=all rust.
The results of the comparative tests on a series of compositions are set forth in Table I. In the illustrative compositions shown in Table I, the mineral lubricating oils employed were hydrofinished oils. The oils contained a small foam inhibiting amount (0.00001 to 0.0001 percent by weight) of a commercial polymethylsiloxane foam inhibitor (DC Fluid 200). i
TABLE I A B C D E F G Make-up, percent by weight:
Mineral lubricating oil A 99.329 99.229 98.673 Mineral lubricating oil B 99. 429 99. 268 99. 278 Mineral lubricating oil C 99. 043 2,6-di-tertiary-butyl-4-methylphenol 0. 596 0. 596 1. 092 0. 496 0. 496 0. 496 0. 547 Cocoamine di-oxo-octyl orthophosphat 0.015 0. 015 0.015 0.015 0.015 0.015 0.016 Dodecenyl succinic anhydride 0. 042 0.042 0. 042 0.042 O. 042 0. 042 0. 048 Dimerized linoleio acid-sorbitan monooleate acid ester 0. 018 0. 018 0. 018 0. 018 0. 018 0. 018 0. 021 Sulfurized sperm oil (approx. 11.5% S) 0. 195 Caprylic acid 0. 1 0. 1 Morpholine 0. 061 0. 03 Morpholine-caprylate 0. 151 Inspections and tests:
Gravity: API 32. 2 32. l 32. 1 31. 1 30. 9 31. 1 29. 4 Viscosity, SUS, D446 at 100 F 153. O 152. 153. 0 208 206 207 407 210 F 44. 0 43. 3 43. 9 47. 2 47. 3 47. 3 68. 9 Viscosity index... 112 98 108 101 104 102 100 Color, D1500 0. 5 0. 5 0. 6 1. 0 1. 0 1. 0 1. 5 Acid number, D6 0. 22 0. 04 0. 58 0. 11 0. 45 0. 41 0. 61 Bust test, D665:
Procedure A Pass Pass Pass Pass Pass Pass Pass Procedure B Pass Pass Pass Pass Pass Pass Vapor space rust test:
Rust rating at 72 hours (=perfect) 12 34 38 I 26 36 9 38. 36. 5 Appearance of copper 1 Fail.
2 Test at 24 hours. 8 Dark brown.
4 White Wax.
Blue crystals.
7 No change.
5 Dark gray wax.
are hung horizontally from holders on the bottom of the loose-fitting stainless steel cover. A 1" x 3" freshly polished copper panel is mounted on the bottom surface of one of these top mounted panels.
Two of these test boxes are inserted in a controlled temperature chamber. The water in the chamber is kept level with the level of the test oil. The water is automatically heated and cooled repeatedly by means of internal coils and is held at 175 F. for four hours, then maintained at 55 F. for four hours. The water bath is cooled from 175 to 55 F. over approximately minutes. The bath is heated from to 175 F. over approximately 45 minutes. The cooling time is considered part of the four hours at 55 F.; likewise, the heating period is part of the four hours at 175 F. During the test period, the water is circulated from the chamber through coils soldered to the The satisfactory rust inhibiting properties for all compositions in contact with the metal according to Rust Test ASTM D665, Procedure A is evident from the data in Table I. It will be noted that Composition D which con: tained neither caprylic acid nor morpholine and no morpholine caprylate failed the Procedure B test of ASTM D665. In addition to the contact rust inhibiting properties of compositions of the invention (Compositions B, C, E, F and G), these compositions also provided excellent vapor space rust inhibition. It will be noted that the base oil compositions (Compositions A and D) which con tained neither caprylic acid nor morpholineand no morpholine caprylate gave very little protection in the Vapor Space Rust Test notwithstanding their ability to provide adequate protection in the ASTM D665, Procedure A evaluation.
' Other lubricating compositions within'the scope of the invention are illustrated in Table H.
14 carboxylic acid that contains to carbon atoms and not more than one ethylenic linkage per molecule.
TABLE II Composition H I J K L M N Make-up: percent by Weight:
Mineral lubricating oil 98. 265 97.00 98. 61 97. 19 98. 58 97. 52 97. 54
Alkyl phenol:
2,6-di-tertiary-butyl-tmethyl phenol 2,4,fi-tri-tertiary-butylphenol Amine salt of diester o-phosphoric acid:
Cocoamine di-oxo-octyl orthopbosphate Oyclohexylamine salt of 3-rnethylbutyl,Z-ethylhexyl orthophosphat Cocoamine salt of 3-methylbutyl, 2-ethylhexyl ortl10ph0sphate n-Octylamino dfoxo-octyl orthophosphate Oxo-octylamine di-oxo-octyl orthophosphate.
Alkenyl-substituted succinic acid anhydride:
Octylenyl succinic anhydride Decenyl succinic anhydride Dodecenyl succinic anhydride Acid ester:
Dimerized linoleic acid-sorbitan monooleate Dimerized linolenic acid-sorbitan trinleate Dimerized linolenic acid-xylitan dioleate-..
Sulfurized monoester:
Sulfurizecl oleyl oleate (approx. 10.7% S) Suliurized oleyl hexadecenoate (approx. 11. 2% S) Sulfurized hexadccyl tetraedecenoate (approx. 6.6% S) Caprylic acid Morpholine- Morpholine-caprylate While our invention is described above with reference to various specific examples and embodiments, it will be understood that the invention is not limited to such examples and embodiments and may be variously practiced within the scope of the claims hereinafter made.
We claim:
1. A lubricating composition comprising a major amount of a hydrocarbon lubricating oil and minor proportions consisting of about 0.1 to about 5.0 percent by weight of an alkyl phenol that contains at least one alkyl group containing 3 to 12 carbon atoms; about 0.001 to about 1.0 percent by weight of an amine salt of a diester of o-phosphoric acid; about 0.01 to about 0.3 percent by weight of an alkenyl-substituted succinic acid anhydride wherein the alkenyl group contains 5 to 18 carbon atoms; about 0.001 to about 1.0 percent by weight of an acid ester of (1) a dimeric acid derived from an unsaturated fatty acid containing 6 to 22 carbon atoms and having 2 to 3 ethylenic linkages per molecule and (2) a partial ester of a fattyacid containing 12 to 24 carbon atoms and an alkitolanhydride; about 0.05 to about 0.2 percent by weight of caprylic acid; and morpholine, said morpholine comprising about 0.5 to about 1.0 times the theoretical amount required to convert the caprylic acid to morpholine caprylate.
2. A lubricating composition comprising a. major amount of a hydrocarbon lubricating oil and minor proportions consisting of about 0.1 to about 5.0 percent by weight of an alkyl phenol, said alkenyl phenol containing at least one tertiary alkyl group containing between 3 and 12 carbon atoms; about 0.001 to about 1.0 percent by weight of an amine salt of a diester of o-phosphoric acid; about 0.01 to about 0.3 percent by weight of an alkenyl-substituted succinic acid anhydride wherein the alkenyl group contains 5 to 18 carbon atoms; about 0.001 to about 1.0 percent by weight of an acid ester of 1) a dimeric acid derived from an unsaturated fatty acid containing 6 to 22 carbon atoms and having 2 to 3 ethylenic linkages per molecule and (2) a partial ester of a fatty acid containing 12 to 24 carbon atoms and an alkitol anhydride; about 0.05 to about 0.2 percent by weight of caprylic acid; morpholine, said morpholine comprising about 0.5 to about 1.0 times the theoretical amount required to convert the caprlyic acid to morpholine caprylate; and abount 0.01 to about 1.0 percent by weight of a sulfurized monoester addition product of sulfur and an unsaturated ester of an aliphatic monohydric alcohol that contains 14 to 20 carbon atoms and not more than one ethylenic linkage per molecule and an aliphatic mono- 3. A lubricating composition comprising a major amount of a hydrocarbon lubricating oil and minor proportions consisting of about 0.1 to about 5.0 percent by weight of an alkyl phenol, said alkyl phenol containing at least one tertiary alkyl group containing between 3 and 12 carbon atoms; about 0.001 to about 1.0 percent by Weight of an amine salt of a dialkyl ester of o-phosphoric acid whose alkyl substituents each contain 3 to 12 carbon atoms; about 0.01 to about 0.3 percent by weight of an alkenyl-substituted succinic acid anhydride wherein the alkenyl group contains 5 to 18 carbon atoms; about 0.001 to about 1.0 percent by weight of an acid ester of (1) a dimeric acid derived from an unsaturated fatty acid containing 6 to 22 carbon atoms and having 2 to 3 ethylenic linkages per molecule and (2) a partial ester of a fatty acid containing 12 to 24 carbon atoms and an alkitol anhydride; about 0.05 to about 0.2 percent by weight of caprylic acid; and morpholine, said morpholine comprising about 0.5 to about 1.0 times the theoretical amount required to convert the caprylic acid to morphoe line caprylate.
4. A lubricating composition comprising a major amount of a hydrocarbon lubricating oil and minor proportions consisting of about 0.1 to about 5.0 percent by weight of any alkyl phenol, said' alkyl phenol containing at least one tertiary alkyl group containing between 3 and 12 carbon atoms; about 0.001 to about 1.0 percent by weight of an amine salt of a dialkyl ester of o-phosphoric acid whose alkyl substituent each. contains 3 to 12 carbon atoms; about 0.01 to about 0.3 percent by weight of an alkenyl-substituted succinic acid anhydride wherein the alkenyl group contains 8 to 12 carbon atoms; about 0.001 to about 1.0 percent by weight of an acid ester of 1) a dimeric acid derived from an unsaturated fatty acid containing 6 to 22 carbon atoms and having 2 to 3 ethylenic linkages per molecule and (2) a partial ester of a fatty acid containing 12 to 24 carbon atoms and an alkitol anhydride; about 0.05 to about 0.2 percent by weight of caprylic acid; and morpholine, said morpholine comprising about 0.5 to about 1.0 times the theoretical amount required to convert the caprylic acid to morpholine caprylate.
5. A lubricating composition comprising a major amount of a hydrocarbon lubricating oil and minor proportions consisting of about 0.1 to about 5.0 percent by weight of an alkyl phenol, said alkyl phenol containing at least one tertiary alkyl group containing between 3 and 12 carbon atoms; about 0.001 to about 1.0 percent by weight of an amine salt of a dialkyl ester of o-phosphoric acid whose alkyl substituents each contains 3 to 12 carbon atoms; about 0.01 to about 0.3 percent by weight of an alkenyl-substituted succinic acid anhydride wherein the alkenyl group contains 8 to 12 carbon atoms; about 0.001 to about 1.0 percent by weight of an acid ester of (1) a dimeric acid derived from an unsaturated fatty acid containing 18 carbon atoms and having from 2 to 3 ethylenic linkages per molecule and (2) a partial ester of a fatty acid containing 18 carbon atoms and a hexitol anhydride; about 0.05 to about 0.2 percent by Weight of caprylic acid; and morpholine, said morpholine comprising about 0.5 to about 1.0 times the theoretical amount required to convert the caprylic acid to morpholine caprylate.
6. A lubricating composition comprising a major amount of a hydrocarbon lubricating oil and minor proportions consisting of about 0.1 to about 5.0 percent by weight of an alkyl phenol, said alkyl phenol containing at least one tertiary alkyl group containing between 3 and 12 carbon atoms; about 0.001 to about 1.0 percent by weight of an amine salt of a dialkyl ester of o-phosphoric acid whose alkyl substituents each contain 3 to 12 carbon atoms; about 0.01 to about 0.3 percent by weight of an alkenyl substituted succinic acid anhydride wherein the alkenyl group contains 8 to 12 carbon atoms; about 0.001 to about 1.0 percent by weight of an acid ester of 1) a dimeric acid derived from an unsaturated fatty acid containing 18 carbon atoms and having from 2 to 3 ethylenic linkages per molecule and (2) a partial ester of a fatty acid containing 18 carbon atoms and a hexitol anhydride; about 0.05 to about 0.2 percent by weight of caprylic acid; morpholine, said morpholine comprising about 0.5 to about 1.0 times the theoretical amount required to convert the caprylic acid to morpholine caprylate; and about 0.01 to about 1.0 percent by weight of sulfurized sperm oil.
7. A lubricating composition comprising a major amount of a hydrocarbon lubricating oil; about 0.1 to about 5.0 percent by weight of 2,6-di-tertiary-butyl-4- methylphenol; about 0.001 to about 1.0 percent by weight of a salt of an aliphatic monoamine containing 6 to 18 carbon atoms and a dialkyl ester of o-phosphoric acid Whose alkyl substituents each contain 3 to 12 carbon atoms; about 0.01 to about 0.3 percent by weight of an alkenyl-substituted succinic acid anhydrate wherein the alkenyl group contains 8 to 12 carbon atoms; about 0.001 to about 1.0 percent by weight of an acid ester of a dimer of linoleic acid and sorbitan monooleate; about 0.05 to about 0.2 percent by weight of caprylic acid; and about 0.015 to about 0.12 percent by weight of morpholine, said morpholine comprising about 0.5 to about 1.0 times the theoretical amount required to convert the caprylic acid to morpholine caprylate.
8. A lubricating composition comprising a major amount of a hydrocarbon lubricating oil; about 0.1 to about 5.0 percent by weight of 2,6-di-tertiary-butyl-4- methylphenol; about 0.001 to about 1.0 percent by weight of the cocoamine salt of di-oxooctyl acid orthophosphate; about 0.01 to about 0.3 percent by weight of dodecenyl succinic anhydride; about 0.001 to about 1.0 percent by weight of an acid ester of a dimer of linoleic acid and sorbitan monooleate; and about 0.05 to about 0.3 percent by weight of morpholine caprylate. I
9. A lubricating composition comprising a major amount of a hydrocarbon lubricating oil; about 0.1 to about 5.0 percent by weight of 2,6-di-tertiary-buty1-4- methylphenol; about 0.001 to about 1.0 percent by weight of the cocoamine salt of di-oxo-octyl acid orthophosphate; about 0.01 to about 0.3 percent by weight of dodccenyl succinic anhydride; about 0.001 to about 1.0 percent by weight of an acid ester of a dimer of linoleic acid and sorbitan monooleate; about 0.05 to about 0.2 percent by Weight of caprylic acid; and about 0.015 to about 0.12 percent by weight of morpholine, said morpholine comprising about 0.5 to about 1.0 times the theoretical amount required to convert the caprylic acid to morpholine caprylate.
10. A lubricating composition comprising a major amount of a hydrocarbon lubricating oil; about 0.1 to about 5.0 percent by weight of 2,6-di-tertiary-butyl-4- methylphenol; about 0.001 to about 1.0 percent by weight of the cocoamine salt of di-oXo-octyl acid orthophosphate; about 0.01 to about 0.3 percent by weight of dodecenyl succinic anhydride; about 0.001 to about 1.0 percent by weight of an acid ester of a dimer of linoleic acid and sorbitan monooleate; about 0.05 to about 0.2 percent by weight of caprylic acid; about 0.015 to about 0.12 percent by weight of morpholine, said morpholine comprising about 0.5 to about 1.0 times the theoretical amount required to convert the caprylic acid to morpholine caprylate; and about 0.01 to about 1.0 percent by weight of sulfurized sperm oil.
References Cited UNITED STATES PATENTS 2,789,950 4/1957 Gottshall et a1 25232.5 2,767,144 10/1956 Gottshall et a1 252-325 2,789,951 4/1957 Kern et a1. 25232.5 2,786,028 3/1957 Gottshall et a1 25232.5 2,789,952 4/1957 Cantrell et a1. 252-32.5
DANIEL E. WYMAN, Primary Examiner I. VAUGHN, Assistant Examiner US. Cl. X.R. 252-34, 78, 392
qggg UMTEED mrmr errrrr Paremr No 31785375 mired January 15 1974 m fl Earl L Humphrey and Willard BO Morse It is certified mm error appeam m the almw ldmrlfmd parent and that said Letrem mraar are hereby wrmcmd m mam below:
Column 3, line 69 "ofr" should read for lines 72 to 75,, R R
R m N should read R N Column 6, lines 60 to 63 that portion of the "formula reading 11 2n--x H2n-x C should read Q OH H l 0 or; r 0
Column '7, line 53 after "invention," insert Accordingly,
they need not be described in detail,
Column 9, line 66 11 should read 11 /1) m Column 13, line '71 "abount ehould read about Column 15 line 45, "anhydrate" e'hould read anhydride -4,
Signed and this Efird dag; of April 197i SEAL) Attest:
IQQWARD I LPLiJTQITEQJRO 0,, MARSHALL DAE-EN' rlrtes'clngg Offloer Gou'mieeioner of Patents Po-ww mush smiias PATENT swim (5/59) v u m @ERTWEQATTE Gi @CGREREQTLEQW Ream No; 3,785,975 hams J nuary 15, 1974 Invfint@f(a) Earl L, Humphrey and Willard Be Morse It is certified that error in the ahsw idamifisai pawns and that said Lefitsrs Pawns are hereby sormsssd as shown hslws F *Column 3, line 69,, "ofr should read M for "7 lines 72 to 75,, R R
R1 N should read R N Columnfi, lines 60 to 63 that portion of the formula reading n 2n-x H2n-x C should read C OH H H O OH 0 Column '7, line 53, after "inventiomfl' insert Accordingly,
they need not be described in detail,
. 9 Column 9, line 66 "n should read 11 /1) Column 13,, line 71 "aloount should read about Column 15, line 45, "anhydrate should read anhydride Signed and sealed this 23rd day of April 1972;
(Sl AL) Attest:
EQUAL) I IBFLATCHEEZ J'RO G O MARSE-IALL DAHN' attesting; Officer Commissioner of Patents Column 3, line 69', "ofr" should read for Po-wfio v, mmq
CEREKQATE @RTE patent 3,785,975 hated January 15, 1974 e Earl L. Humphrey and Willard B, Morse It is certified thQi error appears in she ehow idsmfifmd patent and that said Letters Fa'ssm: are heresy ass-rested as sham slew:
lines 72 to 75, R R
R N should read 6 R N Column 6, lines 60 to 63, that-portion of the formula reading n 2nX H2n i C I should read C OH H l H O OH I 0 Column 7, line 53, after "invention," insert Aocordingly,
they need not be described in detail.
Column 9, line 66, "n should read n /D Column 13, line 71 "abount" should read about Column 15, line 45, "anhydrate" should read anhydride Signed and sealed this 23rd day Of April 19714..
(SEAL) Attest:
ZEJQWARIZ I I.FLET ?HI:1H,JR, Oa MARSl-IALL DAHN Antes slug; Offlcer Commissioner of Patents
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US00154684A Expired - Lifetime US3785975A (en) | 1971-06-18 | 1971-06-18 | Vapor space inhibited turbine oil |
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US4290912A (en) * | 1980-02-21 | 1981-09-22 | Northern Instruments Corporation | Volatile corrosion inhibiting article |
US4308168A (en) * | 1978-09-30 | 1981-12-29 | Idemitsu Kosan Co., Ltd. | Vapor phase corrosion inhibitor compositions and method of inhibiting corrosion using said compositions |
US4514311A (en) * | 1983-05-09 | 1985-04-30 | Texaco Inc. | Wear-resistant aircraft engine lubricating oil |
US4604226A (en) * | 1985-03-22 | 1986-08-05 | E. I. Du Pont De Nemours And Company | Aerosol corrosion inhibitors |
US4655946A (en) * | 1985-11-07 | 1987-04-07 | Exxon Research And Engineering Company | Sea water resistant turbo oil |
US4671933A (en) * | 1985-06-24 | 1987-06-09 | Stauffer-Wacker Silicones Corporation | Method for inhibiting corrosion of metal surfaces |
US5382374A (en) * | 1990-03-31 | 1995-01-17 | Tonen Corporation | Hydraulic fluids for automobile suspensions |
US20040063837A1 (en) * | 2002-01-22 | 2004-04-01 | Kubik Donald Alfons | Tarnish inhibiting composition and article containing it |
US20040069972A1 (en) * | 2002-01-22 | 2004-04-15 | Kubik Donald Alfons | Corrosion inhibiting composition and article containing it |
US20040173779A1 (en) * | 2002-01-22 | 2004-09-09 | Gencer Mehmet A. | Biodegradable shaped article containing a corrosion inhibitor and inert filler particles |
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