US2548493A - Esters of trimethyladipic acid - Google Patents

Esters of trimethyladipic acid Download PDF

Info

Publication number
US2548493A
US2548493A US4232948A US2548493A US 2548493 A US2548493 A US 2548493A US 4232948 A US4232948 A US 4232948A US 2548493 A US2548493 A US 2548493A
Authority
US
Grant status
Grant
Patent type
Prior art keywords
acid
esters
lubricants
trimethyladipic
viscosity
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
Inventor
Richard F Robey
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Standard Oil Development Co
Original Assignee
Standard Oil Development Co
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Grant date

Links

Images

Classifications

    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M1/00Liquid compositions essentially based on mineral lubricating oils or fatty oils; Their use as lubricants
    • C10M1/08Liquid compositions essentially based on mineral lubricating oils or fatty oils; Their use as lubricants with additives
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/16Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation
    • C07C51/31Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation of cyclic compounds with ring-splitting
    • C07C51/316Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation of cyclic compounds with ring-splitting with oxides of nitrogen or nitrogen-containing mineral acids
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C69/00Esters of carboxylic acids; Esters of carbonic or haloformic acids
    • C07C69/34Esters of acyclic saturated polycarboxylic acids having an esterified carboxyl group bound to an acyclic carbon atom
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/28Esters
    • C10M2207/282Esters of (cyclo)aliphatic oolycarboxylic acids
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/28Esters
    • C10M2207/34Esters having a hydrocarbon substituent of thirty or more carbon atoms, e.g. substituted succinic acid derivatives

Description

Patented Apr. 10, 1951 2,548,493 ESTERS F TRIMETHYLADIPIC ACID Richard F. Robey, Cranford, N. .L, assignor to Standard Oil Development Company, a corporation of Delaware No Drawing. Application August 3, 1948,

. 7 Serial No. 42,329

This invention relates to a new class of compoundswhich 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 lubricantsJ Thus, viscosity index improvers and pour depressants are added to automotive lubricants 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 efiort to obtain superior lubricants endowed with specific and superior char--' acteristics, a new field has been explored, namely, the synthesis of lubricants from various materials. Esters represent one class of materials which have attracted unusual interest as syn-.- thetic 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 exhibit these desirable characteristics. Lubricants possessing such properties are of special value in the lubrication of engines which are subjected to high temperatures such as combustion turbine engines, particularly those of the prop-jet type. Mineral oil lubricants containing added viscosity index improvers, thickeners or other highly nonvolatile additives are undesirable for use in such engines because of the tendency to leave a' residue which accumulates and interferes with the operation of the engine. A synthetic lubricant of the type described in the present specification is especially adapted to use under such conditions, since the lubricant contains no additives and thus tends to leave no residue upon volatilization.

It has been found that long chain esters of alkylated adipic acids are suitable for use as synthetic lubricants. These include esters of long chain alkylated adipic acids, e. g., octadecyladipic acid. A more preferred group of esters, notable especially for their high viscosity indices and low pour points, are the fully esterified trimethyladipic acids, wherein the esterifying group is an aliphatic hydrocarbon radical of 1 4 Claims. (Cl. 260-485) Y 2 to 18 carbon atoms, chosen so that the total number of carbon atoms in both esterifying groups is 12 to 36. The esterifying groups may be saturated or unsaturated and maybe of a straight chain or branched chain character. The groups Which esterify thetwo carboxyl groups of the acid may be alike or unlike in chain length or other characteristics.

irimethyladipic acid, which undoubtedly consists of a mixture of the two isomeric forms having the structures may be readily prepared by oxidizing dihydroisophorone with nitric acid, a detailed method for carrying out thepreparationbeing described hereinafter. The trimethyladipic acid may be readily esterified by refluxing with a suitable alcohol in the presence of a catalyst such as p-toluenesulfonic acid monohydrate and a suitable medium ior entraining water during the reaction.

Aliphatic alcohols which are suitable for preparing the esters of the present invention include the primary alcohols, saturated and unsaturated, of the C1 to C18 range, e. g., methyl, ethyl, n-propyl, n-butyl, n amyl, n-hexyl, n-octyl, n-decyl, n-dodecyl, n-tetradecyl, cetyl, oleyl and n-octadecyl alcohols, as well as branched chain primary alcohols, e. g., Z-ethylhexyl alcohol. Another group of alcohols especially adapted for use in connection with the present invention are the so called OX0 alcohols, prepared by the reaction of carbon monoxide and hydrogen upon C2 to C17 olefins obtainable from petroleum sources. Materials such as diisobutylene and polypropylene are suitable for this purpose. The alcohols obtained normally have a branched chain structure.

Data will be given below showing properties of a number of examples of esters of trimethyladipic acid, particularly with respect to their usefulness as synthetic lubricating oils. All of the esters were prepared by esterifying trimethyladipic acid, which was prepared by the following method: In an all-glass apparatus, consisting of a 3-liter flask fitted with a stirrer, condenser, and dropping funnel, was placed 1.5

liters (16 mols) of 50% aqueous nitric acid solu tion. This material was heated to boiling and 350 grams (2.5 mols) of dihydroisophorone was point data for the n-dodecyl esters are given in Table II.

added dropwise at such a rate that refluxing Table H continued rapidly. The refluxin was continued for several hours after the addition of the dihy- Acid Alcohol fan; droisophorone was complete. The resulting solution was nearly neutralized with sodium hy- D droxide, and the top layer resulting from this f mf +36 procedure was separated. After washing the Fj -g product three or four times with a saturated @rietfiiahifiu.---- i ZIIIIdg 32 aqueous sodium chloride solution, benzenewas wa em 2 0 i i iig zg ,2 2 3: 2, as: 1%;: g zgg g The esters of the present invention not only Vacuum tripping to We 307 grams of product possess good lubricating qualities in themselves This material may distilled or used in but they may be also blended with mineral lubricrude state eating oils to give lubricants of improved viscos- Each of the esters described in the table below x22: i gg gg g was prepared by esterifying the trimethyladipic acid obtained in the above described process in fl g fi m m matter hilly accordance with the following procedure which es ed yadlplc acld the eggnfymg is perfectly general in its application: A mixture radlcals bemg alkyl radlcals each P m to containing 1 mol of trimethyladipic acid, 2.2 mols carbon i the two estenfyma radicals of alcohol 07% by Weight of p-toluenesulfoni i r conta ning a total of 12 to 06 carbon oms acid monohydrate, and a water entraimng mate- 25 a rial such as benzene, toluene, naphtha, or the A ff P accordmg to clalm m whlqh like, was refluxed until no more water collected i estelfymg radcals are normal Straight cham in the water trap connected to the refluxing cona gsg g i ggsg g grams 23 2 denser. Then the mixture was washed three dengrl g g laldi s er e times with a saturated solution of sodium car- I As a new Com bonate and once with Water. After drying over d 1 t f t th 1 a e a desiccant such as Drierite (anhydrous 0 ecy es el nme iggifi gg CaSOr), the product was stripped at 210-225 C. under 5 mm. pressure. REFEREN The esters obtained by the above typical reacm CBS CITED tion method were found to have the properties lhe following references are of record in the set forth in Table I. file 0f thls Patent Table I Kinematic Viscosity Oflggd Point Alcohol Used in Esterification fggg gig? g z 25%???23? 100 F. 210 F. a 8 5 F. c. C Oxo alcohol froma 01 olefin 13.790 3.198 108 0. 754 -ss -10 09 0x0 alcohol from d obutylcne 22. 710 4.316 no 0. 751 -35 -10 n-Decanol 16. as 3. 78? 154 0. 724 -35 -l0 n-Dodecanolufi 21. 420 4. 752 158 0. 674 5 -l0 1 A well refined, solventextraeted parafiinic type lubricating oil of SAE-2O viscosity grade.

UNITED STATES PATENTS Name Date Finch Aug. 31, 1948 OTHER REFERENCES Beilstein: Handbuch der organischen Chemie (4th ed.), vol. 2, page 715 (1920), vol. 2, Second supplement, page 605.

Number

Claims (1)

1. AS A NEW COMPOSITION OF MATTER A FULLY ESTERIFIED TRIMETHYLADIPIC ACID, THE ESTERIFYING RADICALS BEING ALKYL RADICALS EACH CONTAINING 1 TO 18 CARBON ATOMS, THE TWO ESTERIFYING RADICALS TOGETHER CONTAINING A TOTAL OF 12 TO 36 CARBON ATOMS.
US2548493A 1948-08-03 1948-08-03 Esters of trimethyladipic acid Expired - Lifetime US2548493A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
US2548493A US2548493A (en) 1948-08-03 1948-08-03 Esters of trimethyladipic acid

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
US2548493A US2548493A (en) 1948-08-03 1948-08-03 Esters of trimethyladipic acid

Publications (1)

Publication Number Publication Date
US2548493A true US2548493A (en) 1951-04-10

Family

ID=21921268

Family Applications (1)

Application Number Title Priority Date Filing Date
US2548493A Expired - Lifetime US2548493A (en) 1948-08-03 1948-08-03 Esters of trimethyladipic acid

Country Status (1)

Country Link
US (1) US2548493A (en)

Cited By (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2839571A (en) * 1955-08-12 1958-06-17 Nat Distillers Chem Corp Ester products
US2852470A (en) * 1954-10-15 1958-09-16 Gen Motors Corp Refrigeration composition
US2866812A (en) * 1956-10-30 1958-12-30 American Oil Co Alkylated esters
DE972646C (en) * 1952-10-24 1959-08-27 Exxon Research Engineering Co synthetic oil we
US2971915A (en) * 1957-02-11 1961-02-14 Shell Oil Co Lubricating oil compositions
DE1107869B (en) * 1958-04-12 1961-05-31 Roehm & Haas Gmbh Additives to hydraulic fluids based on mineraloelfreien Glykolaethern or triaryl
US3003888A (en) * 1957-08-22 1961-10-10 Eastman Kodak Co Plastic compositions containing dicarboxylic acid plasticizers
US3080416A (en) * 1959-01-16 1963-03-05 Continental Oil Co Preparation of esters of substituted adipic acids
DE976185C (en) * 1952-02-16 1963-04-18 Exxon Research Engineering Co synthetic oil we
US4155861A (en) * 1971-05-05 1979-05-22 Studiengesellschaft Aktiengesellschaft Ester lubricant
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
DE102004034202A1 (en) * 2004-07-14 2005-11-10 Sasol Germany Gmbh Ester mixture obtained by esterification of dicarboxylic acid in presence of tri-/tetra-carboxylic acid with mono-hydroxy alcohol, useful as e.g. lubricant, hydraulic fluid, comprises alcohol, carbonic acids and dicarbonic acid
US7018558B2 (en) 1999-06-09 2006-03-28 Cognis Corporation Method of improving performance of refrigerant systems

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2448259A (en) * 1944-10-16 1948-08-31 Shell Dev Unsaturated esters of substituted adipic acid and their production

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2448259A (en) * 1944-10-16 1948-08-31 Shell Dev Unsaturated esters of substituted adipic acid and their production

Cited By (22)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE976185C (en) * 1952-02-16 1963-04-18 Exxon Research Engineering Co synthetic oil we
DE972646C (en) * 1952-10-24 1959-08-27 Exxon Research Engineering Co synthetic oil we
US2852470A (en) * 1954-10-15 1958-09-16 Gen Motors Corp Refrigeration composition
US2839571A (en) * 1955-08-12 1958-06-17 Nat Distillers Chem Corp Ester products
US2866812A (en) * 1956-10-30 1958-12-30 American Oil Co Alkylated esters
US2971915A (en) * 1957-02-11 1961-02-14 Shell Oil Co Lubricating oil compositions
US3003888A (en) * 1957-08-22 1961-10-10 Eastman Kodak Co Plastic compositions containing dicarboxylic acid plasticizers
DE1107869B (en) * 1958-04-12 1961-05-31 Roehm & Haas Gmbh Additives to hydraulic fluids based on mineraloelfreien Glykolaethern or triaryl
US3080416A (en) * 1959-01-16 1963-03-05 Continental Oil Co Preparation of esters of substituted adipic acids
US4155861A (en) * 1971-05-05 1979-05-22 Studiengesellschaft Aktiengesellschaft Ester lubricant
US6666985B2 (en) 1992-06-03 2003-12-23 Cognis Corporation Polyol ester lubricants for hermetically sealed refrigerating compressors
US6296782B1 (en) 1992-06-03 2001-10-02 Henkel Corporation Polyol ester lubricants for refrigerator compressors operating at high temperatures
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
DE102004034202A1 (en) * 2004-07-14 2005-11-10 Sasol Germany Gmbh Ester mixture obtained by esterification of dicarboxylic acid in presence of tri-/tetra-carboxylic acid with mono-hydroxy alcohol, useful as e.g. lubricant, hydraulic fluid, comprises alcohol, carbonic acids and dicarbonic acid

Similar Documents

Publication Publication Date Title
US3429817A (en) Diester lubricity additives and oleophilic liquids containing the same
US3309318A (en) Blends of ester lubricants
US2494366A (en) Production of fatty esters
US2680096A (en) Process for preparing sulfurized polyvalent metal phenates
US2836564A (en) Corrosion inhibitors and compositions containing the same
US2582605A (en) Condensation of beta-hydroxyethyl sulfides with compounds containing hydroxyl groups
US2830020A (en) Lubricating oils thickened with metal salts of cyanuric acid
US3062852A (en) Esters of 2, 2, 4, 4-tetraalkylcyclobutane-1, 3-diols
US2632695A (en) Rust inhibitor for light petroleum products
US3280031A (en) High temperature lubricating oils
US3562300A (en) Liquid neoalkylpolyol esters of mixtures of neo-and straight or branched chain alkanoic acids and their preparation
US2416281A (en) Mineral oil composition
US3341574A (en) Di-(neopentylglycol mononeoheptanoate)azelate
US3414618A (en) Mono-p-tertiary alkyl diarylamines
US2053474A (en) Higher alkyl borates and silicates and process for preparing same
US2750342A (en) Synthetic lubricants
US4053491A (en) Branched-chain aliphatic ester oils
US2911367A (en) Mineral lubricating oil composition
US3202701A (en) Complex ester of mixed dicarboxylic acids, neopentyl glycol and aliphatic alcohols
US2632767A (en) Complex phosphate ester synthetic lubricant
US3282971A (en) Fatty acid esters of polyhydric alcohols
US2526506A (en) Hydrocarbon lubricant containing sulfurized aliphatic borates as stabilizers
US3174931A (en) Grease compositions
US2817673A (en) Tricyclodecane esters
US2531129A (en) Mineral lubricating oil compositions containing dialkyldithio-phosphoric acid-formaldehyde condensation products