US2575195A - Dibasic acid esters and method for producing them - Google Patents

Dibasic acid esters and method for producing them Download PDF

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US2575195A
US2575195A US52428A US5242848A US2575195A US 2575195 A US2575195 A US 2575195A US 52428 A US52428 A US 52428A US 5242848 A US5242848 A US 5242848A US 2575195 A US2575195 A US 2575195A
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oxygen
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carbon atoms
glycol
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Jr Paul V Smith
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C323/00—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M3/00—Liquid compositions essentially based on lubricating components other than mineral lubricating oils or fatty oils and their use as lubricants; Use as lubricants of single liquid substances
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/28—Esters
    • C10M2207/30—Complex esters, i.e. compounds containing at leasst three esterified carboxyl groups and derived from the combination of at least three different types of the following five types of compounds: monohydroxyl compounds, polyhydroxy xompounds, monocarboxylic acids, polycarboxylic acids or hydroxy carboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
    • C10M2209/10—Macromolecular compoundss obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M2209/11—Complex polyesters
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
    • C10M2219/08—Thiols; Sulfides; Polysulfides; Mercaptals
    • C10M2219/082—Thiols; Sulfides; Polysulfides; Mercaptals containing sulfur atoms bound to acyclic or cycloaliphatic carbon atoms
    • C10M2219/084—Thiols; Sulfides; Polysulfides; Mercaptals containing sulfur atoms bound to acyclic or cycloaliphatic carbon atoms containing hydroxy groups; Derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
    • C10M2219/08—Thiols; Sulfides; Polysulfides; Mercaptals
    • C10M2219/082—Thiols; Sulfides; Polysulfides; Mercaptals containing sulfur atoms bound to acyclic or cycloaliphatic carbon atoms
    • C10M2219/085—Thiols; Sulfides; Polysulfides; Mercaptals containing sulfur atoms bound to acyclic or cycloaliphatic carbon atoms containing carboxyl groups; Derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2221/00—Organic macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
    • C10M2221/04—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M2221/043—Polyoxyalkylene ethers with a thioether group
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/08—Resistance to extreme temperature
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/12—Gas-turbines
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/12—Gas-turbines
    • C10N2040/13—Aircraft turbines

Definitions

  • This invention relates to a new class of compounds which have been found to be particularly suitable for use as synthetic lubricants because of their low pour points and high viscosity indices.
  • Esters represent one class of materials which have attracted unusual interest as synthetic lubricants. In general, they are characterized by higher viscosity indices and lower pour points than mineral oils of corresponding viscosity. The esters described in the present specification have been found to exh bit very low pour points and high viscosity indi es. Lubricants possessin such properties are of spe ial value in the lubrication of engines which are subjected to high temperatures such as combustion turbine engines. particu arly those of the prop-jet" type.
  • Mineral oil lubricants containin added viscosity index improvers, thickeners or other highly nonvolatile additives are undesirable for use in su h engines because of the tendency to leave a residue which accumu ates and interferes with the operation of the engine.
  • a synthetic lubricant of the type described in the present specification is especial y adapted to use under such conditions, since t e lubricant contains no additives and thus tends to leave no residue upon volatilization.
  • the new compounds of the present invention which have been found to be particularly suitable for use as lubricating oils are complex esters prepared by reacting one mol of a dibasic acid with one mol of a glycol in such a manner that a half ester is formed, after which the terminal hydroxyl and carboxyl groups are esterified with a mono basic acid and monohydric alcohol, respectively.
  • R is an aliphatic hydrocarbon radical, straight chain or branched, saturated or unsaturated, containing 0 to 26 carbon atoms, or it may be an organic radical consisting of a series of saturated aliphatic hydrocarbon radicals linked by one or more atoms of oxygen or sulfur, or both oxygen and sulfur, provided there are at least two carbon atoms between each pair of oxygen or sulfur atoms, and provided further that the total number of carbon, oxygen and sulfur atoms is from 3 to and the total number of sulfur atoms is not greater than 2.
  • R of the formula represents a glycol radical and may consist of a saturated aliphatic hydrocarbon group, straight chain or branched, containing 2 to 18 carbon atoms, or it may be a series of saturated aliphatic hydrocarbon radicals linked by oxygen or sulfur atoms, or by both oxygen and sulfur atoms, provided there are at least two carbon atoms between each carboxyl group and the nearest oxygen or sulfur atoms and at least two carbon atoms between each oxygen or sulfur atom in the chain, and provided further that the total number of carbon, oxygen and sulfur atoms in the entire R radical is from 5 to 80 and the number of sulfur atoms is not greater than 2.
  • R" of the formula represents a monohydric alcohol residue which may be a saturated or unsaturated aliphatic hydrocarbon radical, either straight chain or branched, containing 1 to 20 carbon atoms, or it may be a series of saturated aliphatic hydrocarbon radicals, straight chain or branched, interlinked by oxygen or sulfur atoms, or both oxy en and sulfur atoms, the total number of carbon, oxygen and sulfur atoms being from 4 to 20.
  • the maximum number of oxygen or sulfur atoms or both in the radical R" is not greater than 5, and there is a chain of at least two carbon atoms between the acid radical and the first oxygen or sulfur atom and a similar chain of at least two carbon atoms between each pair of oxygen or sulfur atoms in the radical.
  • R of the formula represents an aliphatic hydrocarbon radical, straight chain or branched, saturated or unsaturated, containing 1 to 22 carbon atoms, or it may represent a series oi aliphatic hydrocarbon radicals interlinked by 1 to 5 oxygen atoms, there being at least two carbon atoms between each pair of oxygen atoms and at least one carbon atom between the carboxyl group and the nearest oxygen atom, the total number of carbon and oxygen atoms in the radical being from 3 to 22, or it may represent an organic radical. consisting of an aliphatic hydrocarbon chain containing a single interlinked sulfur atom which is separated from the carboxyl group by at least one carbon atom, the total number of carbon and sulfur atoms in the radical being from 3 to 22.
  • the molecular weight of the entire ester should be at least 300 and the viscosity at 210 F. should not be greater than 150 seconds (Saybolt) to provide a product having lubricating properties.
  • the preferred dibasic acids are the straight chain dibasic acids of the para!- finic group having from 6 to 10 carbon atoms per molecule.
  • the preferred monohydric alcohols are the aliphatic primary alcohols, whether straight chain or branched, containing no oxygen or sulfur atoms and having from 6 to 10 carbon atoms per molecule.
  • the preferred monobasic acids are the fatty acids containing 2 to 10 carbon atoms per molecule.
  • the complex esters of this invention may be prepared by reacting one molecular proportion of a dibasic acid with one molecular proportion of a glycol under esteriflcation conditions until only one molecular proportion of water oi. reaction is produced, and thereafter esterifylng the unreacted carboxyl and hydroxyl groups with a monohydric alcohol and a monobasic acid, respectively.
  • a method suitable for carrying out the process in detail will be described below in connection with specific examples.
  • dibasic acids which may be employed in the synthesis of the complex esters or the present invention are the following:
  • glycols employed in preparing the esters of the present invention include ethylene glycol and any of the paraflinic homologues of the same containing up to 18 carbon atoms. These may include, for example, ethylene glycol, propylene glycol, butylene glycols, pinacone, trimethylene glycol, tetramethylene glycol, pentamethylene glycol, and the like.
  • glycols may also contain oxygen or sulfur atoms, compounds such 4 as dlethylene glycol, triethylene glycol, the polyethylene glycols of the formula HO (CHzCHzO) .CHzCHzOH where n is 1 to 26, and the polypropylene glycols 01 the general formula where either R1 or R2 is a methyl group and the other is hydrogen, and where n is 1 to 20, may likewise be employed.
  • Glycols containing sulfur atoms in thioether linkages may also be employed, and these include such compounds as thiodiglycol and 1,2 bis(2 hydroxyethylmercapto) ethane.
  • glycols containing both oxygen and sulfur in similar linkages such a compound is bis- [2-(2-hydroxyethoxy) ethyl] sulfide.
  • the monohydric alcohols employed are typified by the following:
  • a group of alcohols especially adapted for use in connection with the present invention are the sc-called "0xo alcohols, prepared by the reaction of carbon monoxide and hydrogen upon the olefins obtainable from petroleum products. Materials such as diisobutylene and C1 olefins are suitable for this purpose; also higher molecular weight olefinic materials are sometimes employed.
  • the alcohols obtained in this manner normally have a branched chain structure.
  • esters of the present invenp-Ethylmercaptopropionic acid tion may also be blended with mineral lubricating fl-Tert-- y m pwpropionic acid oils to give lubricants or improved viscosity index fi-Tert.dodecylmercaptopropionic acid and pour point.
  • esters of the present invention A5 a new composition compound for the purpose of improving their properties of the formulawith respect to their usefulness as lubricants. coon"
  • antioxidants For example, antioxidants, viscosity index improvers, thickeners, pour depressants, dyes, etc., may be added.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Lubricants (AREA)

Description

Patented Nov. 13, 1951 DIBASIC ACID ESTERS AND METHOD FOR PRODUCING THEM Paul VQSmith, Jr., Westfield. N. J., assignor to Standard Oil Development Company, a corporation of Delaware N Drawing. Application October 1, 1948, Serial No. 52,428
8 Claims.
This invention relates to a new class of compounds which have been found to be particularly suitable for use as synthetic lubricants because of their low pour points and high viscosity indices.
In the lubricant art, considerable progress has been realized in recent years in the production of lubricants characterized by one or more specific properties and adapted for particular uses. In the main, this progress can be attributed to two developments: the first, new refining procedures, and the second, addition agents capable of imparting particular properties to available lubricants. Thus, viscosity index improvers and pour depressants are added to automotive lubricanis to render the lubricants more adaptable to wide changes in temperature conditions, while other agents are added to improve the load carrying properties of a lubricant which is to be employed, for example, under extreme pressure conditions.
Recently, in an effort to obtain superior lubricants endowed with specific and superior characteristics, a new field has been explored, namely the synthesis of lubricants from various materia s. Esters represent one class of materials which have attracted unusual interest as synthetic lubricants. In general, they are characterized by higher viscosity indices and lower pour points than mineral oils of corresponding viscosity. The esters described in the present specification have been found to exh bit very low pour points and high viscosity indi es. Lubricants possessin such properties are of spe ial value in the lubrication of engines which are subjected to high temperatures such as combustion turbine engines. particu arly those of the prop-jet" type. Mineral oil lubricants containin added viscosity index improvers, thickeners or other highly nonvolatile additives are undesirable for use in su h engines because of the tendency to leave a residue which accumu ates and interferes with the operation of the engine. A synthetic lubricant of the type described in the present specification is especial y adapted to use under such conditions, since t e lubricant contains no additives and thus tends to leave no residue upon volatilization.
The new compounds of the present invention which have been found to be particularly suitable for use as lubricating oils are complex esters prepared by reacting one mol of a dibasic acid with one mol of a glycol in such a manner that a half ester is formed, after which the terminal hydroxyl and carboxyl groups are esterified with a mono basic acid and monohydric alcohol, respectively.
More precisely, the new class of compounds may be defined by the following general formula:
COOR" where R is an aliphatic hydrocarbon radical, straight chain or branched, saturated or unsaturated, containing 0 to 26 carbon atoms, or it may be an organic radical consisting of a series of saturated aliphatic hydrocarbon radicals linked by one or more atoms of oxygen or sulfur, or both oxygen and sulfur, provided there are at least two carbon atoms between each pair of oxygen or sulfur atoms, and provided further that the total number of carbon, oxygen and sulfur atoms is from 3 to and the total number of sulfur atoms is not greater than 2. R of the formula represents a glycol radical and may consist of a saturated aliphatic hydrocarbon group, straight chain or branched, containing 2 to 18 carbon atoms, or it may be a series of saturated aliphatic hydrocarbon radicals linked by oxygen or sulfur atoms, or by both oxygen and sulfur atoms, provided there are at least two carbon atoms between each carboxyl group and the nearest oxygen or sulfur atoms and at least two carbon atoms between each oxygen or sulfur atom in the chain, and provided further that the total number of carbon, oxygen and sulfur atoms in the entire R radical is from 5 to 80 and the number of sulfur atoms is not greater than 2. R" of the formula represents a monohydric alcohol residue which may be a saturated or unsaturated aliphatic hydrocarbon radical, either straight chain or branched, containing 1 to 20 carbon atoms, or it may be a series of saturated aliphatic hydrocarbon radicals, straight chain or branched, interlinked by oxygen or sulfur atoms, or both oxy en and sulfur atoms, the total number of carbon, oxygen and sulfur atoms being from 4 to 20. The maximum number of oxygen or sulfur atoms or both in the radical R" is not greater than 5, and there is a chain of at least two carbon atoms between the acid radical and the first oxygen or sulfur atom and a similar chain of at least two carbon atoms between each pair of oxygen or sulfur atoms in the radical. R of the formula represents an aliphatic hydrocarbon radical, straight chain or branched, saturated or unsaturated, containing 1 to 22 carbon atoms, or it may represent a series oi aliphatic hydrocarbon radicals interlinked by 1 to 5 oxygen atoms, there being at least two carbon atoms between each pair of oxygen atoms and at least one carbon atom between the carboxyl group and the nearest oxygen atom, the total number of carbon and oxygen atoms in the radical being from 3 to 22, or it may represent an organic radical. consisting of an aliphatic hydrocarbon chain containing a single interlinked sulfur atom which is separated from the carboxyl group by at least one carbon atom, the total number of carbon and sulfur atoms in the radical being from 3 to 22. The molecular weight of the entire ester should be at least 300 and the viscosity at 210 F. should not be greater than 150 seconds (Saybolt) to provide a product having lubricating properties.
Among the various components of the complex esters of the present invention certain preferences may be pointed out as giving the optimum of desired properties from thestandpoint of service as a lubricant. The preferred dibasic acids are the straight chain dibasic acids of the para!- finic group having from 6 to 10 carbon atoms per molecule. The preferred monohydric alcohols are the aliphatic primary alcohols, whether straight chain or branched, containing no oxygen or sulfur atoms and having from 6 to 10 carbon atoms per molecule. The preferred monobasic acids are the fatty acids containing 2 to 10 carbon atoms per molecule.
The complex esters of this invention may be prepared by reacting one molecular proportion of a dibasic acid with one molecular proportion of a glycol under esteriflcation conditions until only one molecular proportion of water oi. reaction is produced, and thereafter esterifylng the unreacted carboxyl and hydroxyl groups with a monohydric alcohol and a monobasic acid, respectively. A method suitable for carrying out the process in detail will be described below in connection with specific examples.
Illustrative examples of the dibasic acids which may be employed in the synthesis of the complex esters or the present invention are the following:
Oxalic acid Malonic acid Succinic acid Glutaric acid Adipic acid Pimelic acid Suberic acid Azelaic acid Sebacic acid Brassylic acid Pentadecanedicarboxylic acid Tetracosanedicarboxylic acid (fl-C24 alkenylsuccinic acids Diglycolic acid Thiodiglycolic acid The C4C2-i alkenylsuccinic acids listed above are prepared by condensing olefins or mixtures of olefins with maleic anhydride.
The glycols employed in preparing the esters of the present invention include ethylene glycol and any of the paraflinic homologues of the same containing up to 18 carbon atoms. These may include, for example, ethylene glycol, propylene glycol, butylene glycols, pinacone, trimethylene glycol, tetramethylene glycol, pentamethylene glycol, and the like. Since the glycols may also contain oxygen or sulfur atoms, compounds such 4 as dlethylene glycol, triethylene glycol, the polyethylene glycols of the formula HO (CHzCHzO) .CHzCHzOH where n is 1 to 26, and the polypropylene glycols 01 the general formula where either R1 or R2 is a methyl group and the other is hydrogen, and where n is 1 to 20, may likewise be employed. Glycols containing sulfur atoms in thioether linkages may also be employed, and these include such compounds as thiodiglycol and 1,2 bis(2 hydroxyethylmercapto) ethane. There also may be used glycols containing both oxygen and sulfur in similar linkages; such a compound is bis- [2-(2-hydroxyethoxy) ethyl] sulfide.
The monohydric alcohols employed are typified by the following:
Methyl alcohol Ethyl alcohol n-Butyl alcohol n-Hexyl alcohol n-Octyl alcohol Z-ethylhexyl alcohol Cetyl alcohol Oleyl alcohol Ethylene glycol mono-n-butyl ether Ethylene glycol mono-2-ethylbutyl ether Ethylene glycol mono-Z-ethylhexyl ether Ethylene glycol mono-tert.-octyl ether p-n-Butylmercaptoethanol p-tert-Octylmercaptoethanol fl-n-Dodecylmercaptoethanol Diethylene glycol monon-butyl ether Diethylene glycol mono-2-ethylbutyl ether Diethylene glycol mono-2-ethylhexyl ether Propylene glycol mono-butyl thioether Propylene glycol mono-tert.-octyl thioether Propylene glycol mono-n-dodecyl thioether n-Butylmercaptoethoxyethanol tert.-Octylmercaptoethoxyethanol n-Dodecylmercaptoethoxyethanol n-Butylmercaptopropoxypropanol tert.-Octylmercaptopropoxypropanol n-Dodecy1mercaptopropoxypropanol Propylene glycol mono-n-butyl ether Dipropylene glycol monomethyl ether Dipropylene glycol monoethyl ether Dipropylene glycol mono-n-butyl ether Tripropylene glycol monomethyl ether Tripropylene glycol monoethyl ether Tripropylene glycol mono-n-butyl ether Propylene glycol monoisopropyl ether Dipropylene glycol monoisopropyl ether Tripropylene glycol monoisopropyl ether Many of the above listed ether alcohols, formed by the reaction of ethylene oxide or propylene oxide with aliphatic alcohols, are known in the industry as Dowanols, Carbitols, or Cellosolves."
A group of alcohols especially adapted for use in connection with the present invention are the sc-called "0xo alcohols, prepared by the reaction of carbon monoxide and hydrogen upon the olefins obtainable from petroleum products. Materials such as diisobutylene and C1 olefins are suitable for this purpose; also higher molecular weight olefinic materials are sometimes employed. The alcohols obtained in this manner normally have a branched chain structure.
6 Among the monobasic acids which may be emmore water collected. The mixture was washed ployed in the preparation of the esters of the with three 100 ml. portions oi saturated sodium present invention. the following m y be listed as carbonate solution and one 100 ml. portion of illustrative: water. After drying over "Drlerlte" '(anhydrous Acetic acid calcium sulfate). the material was filtered and n i l acid stripped to a bath temperature of 200-225 C. at Butyric acid I a pressure of about 5 mm. V leri a id The results of tests of various properties of Caproic acid esters prepared by the above general method are Caprylic acid shown in Table I.
Table I i mash Kinematic Viscosity ASTM' Component oi Ester Point MW PM! P 100 F. 210 r. on Index 5 again: tad"--. l gg fi flfl g 355 45.120 0.050 0.1m n1 so 2-EthylhsxanoL. Adipic acid r 400 satao 1.242 0.03s 14: -8s
no less; use 0.0m 1m -as 400 38.510 1.055 cm 155 -is 410 um 10.40:; am no -ss (i -(Z Alkenylsuccinlc acid.. 'i'figgfi fifi'fk 515 62.155 0.049 0.004 125 ss Metl/yi alcohol C Alkenylsucclniacid g 'figi fififf (3 390 57.952 am am 12s Met yl alcohol..- Sehscic acid igg flgggtgf ff; 300 25.410 5.651 ass-1 162 15 C15- 1] "0X0" 8100b Laurie acid The above data indicate that the esters consti- Palmitic acid tilting the subject-matter of the present invention stearic acid possess characteristics, particularly with regard Oleic acid to viscosity index and pour point, which indicate p-Methoxypropionic acid their suitability for general use as lubricating oils p-Ethoxypropionic acid and particularly for use where the use or additives p-Tert-octoxypropionic acid is not desirable. The esters of the present invenp-Ethylmercaptopropionic acid tion may also be blended with mineral lubricating fl-Tert-- y m pwpropionic acid oils to give lubricants or improved viscosity index fi-Tert.dodecylmercaptopropionic acid and pour point.
If desired, various addition agents may be inwhat is claimed is: corporated in the esters of the present invention A5 a new composition compound for the purpose of improving their properties of the formulawith respect to their usefulness as lubricants. coon" For example, antioxidants, viscosity index improvers, thickeners, pour depressants, dyes, etc., may be added.
Data will be given below showing the propern' ties of several examples of complex esters within m the scope of the present invention indicating the adaptability of these esters to lubricating WhereRis an aliphatic hydrocarbon radical conservice. All of these esters were prepared by a taining 2 to 8 carbon atoms in a straight chain general esterification method which was carried between the COO groups, where R is a radiout in detail as follows: In a 1-liter round botcal of the formula -(CH:CH:O) nCH2CH:-, tomed reaction flask, fitted with a reflux conwhere n is an integer from 1 to 7; where R" is denser and water trap, was placed a charge conan alkyl group containing 1 to 19 carbon atoms; sisting of 1 mol of dibasic acid, 1 incl oi glycol, nd Where R' is an alkyl group containing 3 to 7 4.5 gr. of p-toluenesulfonic acid monohydrate, carbon atoms.
and 100 ml. of toluene. The mixture was re- 2. A composition according to claim 1 in which fluxed until exactly one mol of water was col- Ris aradical containing-i carbon atoms.
lected in the trap. Then, after cooling, 1 mol of 3. A composition according to claim 1 in which monohydric alcohol was added and the reaction R is a radical containing 4 carbon atoms and R" continued until no more water collected in the is a 2-ethylhexyl radical. trap. One mol of monobasic acid was then 4. Acomposition according to claim 1 inwhich added and the reaction continued until again no R is a radical containing 4 carbon atoms, R" is a 2-ethylhexyl radical. and R'" is an n- -D Y radical.
5. A composition according to claim 1 in which R is the radical (CH2CH20) :CHaCHz- 6. A composition according to claim 1 in'which R. is the radical (CH2CH2O) :CHaCI-Ia- 7. A method which comprises reacting one molecular proportion of a polyethylene glycol with one molecular proportion of adipic acid, under conditions which provide for the removal of water formed in the reaction from the reaction zone, until only one molecular proportion of water of reaction is formed and removed, and thereafter adding one molecular proportion of 2-ethylhexanol to the reaction mixture and continuing the esteriflcation reaction until no more water is formed, and thereafter adding one molecular proportion or n-caproic acid and continuing the esterification reaction until again no more water of reaction is formed.
8. A method according to claim '7 in which the glycol employed is triethyiene glycol.
PAUL V. sm'm, Jl.
REFERENCES CITED Y The following references are of record in th file of this patent:
UNITED STATES PATENTS Number Name Date 1,786,404 Young Dec. 23, 1930 2,035,528 Brubaker Mar. 31, 1938 2,073,031 Sly Mar. 9, 1937

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1. AS A NEW COMPOSITION OF MATTER A COMPOUND OF THE FORMULA-
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Cited By (28)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2705724A (en) * 1951-05-24 1955-04-05 Exxon Research Engineering Co Reduction of acidity in synthetic ester lubes with olefin oxides
US2712527A (en) * 1952-08-26 1955-07-05 Exxon Research Engineering Co Improved lubricating greases containing dihydroxy stearic acid soap
US2723957A (en) * 1952-02-27 1955-11-15 Exxon Research Engineering Co Synthetic lubricating oils containing paraffinic resins
US2750341A (en) * 1951-12-28 1956-06-12 Exxon Research Engineering Co Lubricating grease comprising a synthetic oil and a complex thickener
US2751351A (en) * 1952-07-05 1956-06-19 Exxon Research Engineering Co Complex ester base lubricating grease compositions
US2768139A (en) * 1952-10-20 1956-10-23 Exxon Research Engineering Co Lubricating greases from oxo glycols
US2782166A (en) * 1949-05-07 1957-02-19 Exxon Research Engineering Co Ester base lubricating greases
US2820815A (en) * 1954-04-08 1958-01-21 Exxon Research Engineering Co Synthetic lubricating compositions and process for their preparation
US2836565A (en) * 1953-09-17 1958-05-27 Wakefield & Co Ltd C C Lubricating compositions
US2926139A (en) * 1952-11-08 1960-02-23 Bayer Ag Lubricants for refrigerating systems
US2931837A (en) * 1956-04-13 1960-04-05 Union Carbide Corp Long chain alkoxy-diols
US2977331A (en) * 1955-10-20 1961-03-28 Upson Co Process of stabilizing cellulose by impregnation with a salt of an organic basic nitrogen compound containing a hydroxyl group and a partial ester of a polyhydric alcohol and polycarboxylic acid and product thereof
US3048623A (en) * 1957-11-01 1962-08-07 Exxon Research Engineering Co Preparation of complex diester synthetic lubricants
US3381022A (en) * 1963-04-23 1968-04-30 Lubrizol Corp Polymerized olefin substituted succinic acid esters
US3857865A (en) * 1973-08-01 1974-12-31 Emery Industries Inc Ester lubricants suitable for use in aqueous systems
US4122057A (en) * 1974-09-03 1978-10-24 Emery Industries, Inc. Mixed-terminated polyester plasticizers
US4661622A (en) * 1984-09-21 1987-04-28 Satoshi Matsumoto Method for producing composite ester
US4909952A (en) * 1989-01-03 1990-03-20 The Lubrizol Corporation Sulfur-containing polymeric polyesters and additive concentrates and lubricating oils containing same
US5047576A (en) * 1987-03-25 1991-09-10 Showa Denko Kabushiki Kaisha Polymerizable vinyl compound having polythioether skeleton
US5820777A (en) * 1993-03-10 1998-10-13 Henkel Corporation Blended polyol ester lubricants for refrigerant heat transfer fluids
US5851968A (en) * 1994-05-23 1998-12-22 Henkel Corporation Increasing the electrical resistivity of ester lubricants, especially for use with hydrofluorocarbon refrigerants
US5906769A (en) * 1992-06-03 1999-05-25 Henkel Corporation Polyol ester lubricants for refrigerating compressors operating at high temperatures
US5976399A (en) * 1992-06-03 1999-11-02 Henkel Corporation Blended polyol ester lubricants for refrigerant heat transfer fluids
US6183662B1 (en) 1992-06-03 2001-02-06 Henkel Corporation Polyol ester lubricants, especially those compatible with mineral oils, for refrigerating compressors operating at high temperatures
US6221272B1 (en) 1992-06-03 2001-04-24 Henkel Corporation Polyol ester lubricants for hermetically sealed refrigerating compressors
US7018558B2 (en) 1999-06-09 2006-03-28 Cognis Corporation Method of improving performance of refrigerant systems
WO2012166571A1 (en) 2011-05-27 2012-12-06 Exxonmobil Research And Engineering Company A method for producing a two phase lubricant composition
WO2012166575A1 (en) 2011-05-27 2012-12-06 Exxonmobil Research And Engineering Company Oil-in-oil compositions and methods of making

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Publication number Priority date Publication date Assignee Title
GB778132A (en) * 1953-07-02 1957-07-03 Exxon Research Engineering Co Improvements in or relating to the production of complex esters
DE1011109B (en) * 1955-12-19 1957-06-27 Geigy Co Ltd lubricant
DE1230511B (en) * 1963-04-29 1966-12-15 Rheinpreussen Ag Lubricating oil for aircraft gas turbines
DE1246921B (en) * 1964-05-05 1967-08-10 Rheinpreussen Ag Lubricating oils for high-speed aircraft with jet or gas turbine propulsion
FR1561251A (en) * 1968-01-12 1969-03-28

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US1786404A (en) * 1927-10-31 1930-12-23 Young Hoylande Denune Derivative of glycol
US2035528A (en) * 1932-04-16 1936-03-31 Du Pont Synthetic resin
US2073031A (en) * 1935-05-03 1937-03-09 Du Pont Esters of octadecanediol

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US1786404A (en) * 1927-10-31 1930-12-23 Young Hoylande Denune Derivative of glycol
US2035528A (en) * 1932-04-16 1936-03-31 Du Pont Synthetic resin
US2073031A (en) * 1935-05-03 1937-03-09 Du Pont Esters of octadecanediol

Cited By (33)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2782166A (en) * 1949-05-07 1957-02-19 Exxon Research Engineering Co Ester base lubricating greases
US2705724A (en) * 1951-05-24 1955-04-05 Exxon Research Engineering Co Reduction of acidity in synthetic ester lubes with olefin oxides
US2750341A (en) * 1951-12-28 1956-06-12 Exxon Research Engineering Co Lubricating grease comprising a synthetic oil and a complex thickener
US2723957A (en) * 1952-02-27 1955-11-15 Exxon Research Engineering Co Synthetic lubricating oils containing paraffinic resins
US2751351A (en) * 1952-07-05 1956-06-19 Exxon Research Engineering Co Complex ester base lubricating grease compositions
US2712527A (en) * 1952-08-26 1955-07-05 Exxon Research Engineering Co Improved lubricating greases containing dihydroxy stearic acid soap
US2768139A (en) * 1952-10-20 1956-10-23 Exxon Research Engineering Co Lubricating greases from oxo glycols
US2926139A (en) * 1952-11-08 1960-02-23 Bayer Ag Lubricants for refrigerating systems
US2836565A (en) * 1953-09-17 1958-05-27 Wakefield & Co Ltd C C Lubricating compositions
US2820815A (en) * 1954-04-08 1958-01-21 Exxon Research Engineering Co Synthetic lubricating compositions and process for their preparation
US2977331A (en) * 1955-10-20 1961-03-28 Upson Co Process of stabilizing cellulose by impregnation with a salt of an organic basic nitrogen compound containing a hydroxyl group and a partial ester of a polyhydric alcohol and polycarboxylic acid and product thereof
US2931837A (en) * 1956-04-13 1960-04-05 Union Carbide Corp Long chain alkoxy-diols
US3048623A (en) * 1957-11-01 1962-08-07 Exxon Research Engineering Co Preparation of complex diester synthetic lubricants
US3381022A (en) * 1963-04-23 1968-04-30 Lubrizol Corp Polymerized olefin substituted succinic acid esters
US3857865A (en) * 1973-08-01 1974-12-31 Emery Industries Inc Ester lubricants suitable for use in aqueous systems
US4122057A (en) * 1974-09-03 1978-10-24 Emery Industries, Inc. Mixed-terminated polyester plasticizers
US4661622A (en) * 1984-09-21 1987-04-28 Satoshi Matsumoto Method for producing composite ester
US5047576A (en) * 1987-03-25 1991-09-10 Showa Denko Kabushiki Kaisha Polymerizable vinyl compound having polythioether skeleton
US4909952A (en) * 1989-01-03 1990-03-20 The Lubrizol Corporation Sulfur-containing polymeric polyesters and additive concentrates and lubricating oils containing same
US6296782B1 (en) 1992-06-03 2001-10-02 Henkel Corporation Polyol ester lubricants for refrigerator compressors operating at high temperatures
US6666985B2 (en) 1992-06-03 2003-12-23 Cognis Corporation Polyol ester lubricants for hermetically sealed refrigerating compressors
US5906769A (en) * 1992-06-03 1999-05-25 Henkel Corporation Polyol ester lubricants for refrigerating compressors operating at high temperatures
US5976399A (en) * 1992-06-03 1999-11-02 Henkel Corporation Blended polyol ester lubricants for refrigerant heat transfer fluids
US6183662B1 (en) 1992-06-03 2001-02-06 Henkel Corporation Polyol ester lubricants, especially those compatible with mineral oils, for refrigerating compressors operating at high temperatures
US6221272B1 (en) 1992-06-03 2001-04-24 Henkel Corporation Polyol ester lubricants for hermetically sealed refrigerating compressors
US6551524B2 (en) 1992-06-03 2003-04-22 Cognis Corporation Polyol ester lubricants, especially those compatible with mineral oils, for refrigerating compressors operating at high temperatures
US5820777A (en) * 1993-03-10 1998-10-13 Henkel Corporation Blended polyol ester lubricants for refrigerant heat transfer fluids
US5851968A (en) * 1994-05-23 1998-12-22 Henkel Corporation Increasing the electrical resistivity of ester lubricants, especially for use with hydrofluorocarbon refrigerants
US6551523B1 (en) 1995-06-07 2003-04-22 Cognis Corporation Blended polyol ester lubricants for refrigerant heat transfer fluids
US7018558B2 (en) 1999-06-09 2006-03-28 Cognis Corporation Method of improving performance of refrigerant systems
WO2012166571A1 (en) 2011-05-27 2012-12-06 Exxonmobil Research And Engineering Company A method for producing a two phase lubricant composition
WO2012166575A1 (en) 2011-05-27 2012-12-06 Exxonmobil Research And Engineering Company Oil-in-oil compositions and methods of making
US8623796B2 (en) 2011-05-27 2014-01-07 Exxonmobil Research And Engineering Company Oil-in-oil compositions and methods of making

Also Published As

Publication number Publication date
GB662650A (en) 1951-12-12
FR990983A (en) 1951-09-28

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