US3290242A - Metal antioxidants for fluoroesters - Google Patents

Metal antioxidants for fluoroesters Download PDF

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US3290242A
US3290242A US274064A US27406463A US3290242A US 3290242 A US3290242 A US 3290242A US 274064 A US274064 A US 274064A US 27406463 A US27406463 A US 27406463A US 3290242 A US3290242 A US 3290242A
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fluoroesters
metal
fluoroester
antioxidants
acid
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Ravner Harold
Carter O Timmons
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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
    • C10M175/00—Working-up used lubricants to recover useful products ; Cleaning
    • C10M175/0091—Treatment of oils in a continuous lubricating circuit (e.g. motor oil system)
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/48—Separation; Purification; Stabilisation; Use of additives
    • C07C67/62—Use of additives, e.g. for stabilisation
    • 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
    • C10M169/00—Lubricating compositions characterised by containing as components a mixture of at least two types of ingredient selected from base-materials, thickeners or additives, covered by the preceding groups, each of these compounds being essential
    • C10M169/04—Mixtures of base-materials and additives
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2601/00—Systems containing only non-condensed rings
    • C07C2601/06—Systems containing only non-condensed rings with a five-membered ring
    • C07C2601/08—Systems containing only non-condensed rings with a five-membered ring the ring being saturated
    • 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
    • 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
    • C10M2207/125—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
    • C10M2207/127—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 polycarboxylic
    • 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
    • C10M2211/00—Organic non-macromolecular compounds containing halogen as ingredients in lubricant compositions
    • C10M2211/04—Organic non-macromolecular compounds containing halogen as ingredients in lubricant compositions containing carbon, hydrogen, halogen, and oxygen
    • C10M2211/044—Acids; Salts or esters thereof
    • C10M2211/0445—Acids; Salts or esters thereof used as base material
    • 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
    • C10N2030/10—Inhibition of oxidation, e.g. anti-oxidants
    • 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
    • C10N2040/08—Hydraulic fluids, e.g. brake-fluids
    • 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
    • C10N2040/25—Internal-combustion engines

Definitions

  • Fluid neutral esters of omega-hydroperfluoroalkylcarbinols and saturated aliphatic hydrocarbon polycarboxylic acids have been heretofore suggested as a source of potential high temperature lubricants and hydraullc fluids. As a class these esters lack the necessary oxidation stability which would allow their use as lubricants or as hydraulic fluids at temperatures in the range of about 400 to 500 F. p
  • antioxidants which impart an exceptional degree of oxidation stability at elevated temperatures in the range of about 400 to 500 F. to fluid neutral esters of omegahydroperfluorolkylcarbinols which have from 5 to 11 carbon atoms and saturated aliphatic hydrocarbon ditriand tetracarboxylic acids which have from 3 to 9 carbon atoms in the hydrocarbon groups.
  • the metals which we have found to be antioxidants for the fluoroesters of the aforedefined group are barium, tin and zinc.
  • the threshold temperature for antioxidant activity of the metals in the fluoroesters is about 400 F. Below this temperature, the fluoroesters are in themselves oxidation stable.
  • the metals are effective as antioxidants even in small concentrations, as low as on the order of from about 0.05 to 0.5% by weight based on the weight of the fluoroesters, to impart a high order of oxidation stability to the fluoroesters at temperatures in the range of from about 400 to 500 F.
  • the antioxidant metal may be brought into contact with the fluoroesters not only in particle form but also in the form of plates or other larger shapes or configurations as found suitable.
  • the surface of the parts of engines or of other mechanisms with which the fluoroesters come into contact, such as oil lines, may consist of the antioxidant metal or a by-pass system may contain the antioxidant metal in the form of a wire mesh or as a confined mass of grandules through which the fluoroester flows in contact before returning to areas of lubrications.
  • the fluid neutral fluoroesters with which the present invention is concerned may be prepared in known way as as described in Ind. Eng. Chem. 48, 445 (1956) from the omega-hydroperfluoroalkylcarbinols of the general formula:
  • the neutral fluoroesters may be derived by the complete esterification of, for example, glutaric, adipic, pimelic, suberic, azelaic, sebacic and undecanedioc acids; methyl succinic, S-methylglutaric, 1,4-dimethyl adipic, 2,2-dimethyladipic, l-methyl-4-ethyl adipic acids, etc.; camphoric acid, tricarballylic acid, butane-1,2,4-tricarboxylic acid, butane 1,1,4-tricarboxylic acid, etc., and butane-1,2,4,4-tetracarboxylic acid, butane-l,l,2,3-tetracarboxylic acid, butane-l,1,2,3-tetracarboxylic acid, etc.
  • fluid neutral fluoroesters are those described in Ind. Eng. Chem. 48, 445, above, for example, bis (1H,lH,5I-I- octafiuoropentyl)- and his (1H,1H,7H-dodecafluoroheptyl) 3-methylglutarates, bis (1H,1H,5H-octafiuoropentyl) adipate and sebacate, tri (1H,1H,5H-octafluoropentyl) tricarballylate, etc.
  • the antioxidant activity of the metals for the fluoroesters may be evaluated in terms of increase in the viscosity and rise in the neutralization number of the fluoroesters and the amount of fluoride evolved from the fluoroesters. The lower the value for these factors, the greater in general the oxidation stability imparted to the fluoroesters by the metals at a given temperature in the aforesaid range. Depending upon the conditions of service use, all or less than all of these factors may govern in the selection of the fluoroesters on the basis of oxidation stability.
  • Each of the cells is equipped with a watercooled condenser fitted to the top thereof and has a rubber hose connected from the condenser to a separate water trap. Sealed to the upper wall of each of the cells is a means for delivering bubbled air into the bottom of the fluoroester samples in the cells.
  • the cells containing the fluoroester samples and metal specimens and the cell with the control sample are placed in snugly fitting holesi0.5 F. Clean dry air, free from CO is bubbled through the heated fluoroester samples in the cells at a predetermined volume and rate.
  • the efiluent gases from each of the cells which have passed through the individual associated condenser are led into the water trap provided therefor and the fluoride content of the trap liquid determined by the lead chloro-fluoride method.
  • the amount of evolved fluoride is reported as mg. of fluorine per gram of the fluoroester.
  • the viscosity in centistokes at 100 F. and the neutralization number of the fluoroesters are determined before and after the test.
  • the neutralization number is the number of milligrams of potassium hydroxide required to neutralize the fluoroester.
  • composition comprising a fluid neutral ester of a fluoroalcohol of the general formula:
  • n is an integer from 2 to 5 and an aliphatic polycarboxylic acid of the general formula:
  • n is an integer from 2 to 4 and R is a saturated aliphatic hydrocarbon group having from 3 to 9 carbon atoms and a metal of the group consisting of barium, tin and zinc present therein in amount suflicient to improve the oxidation stability of the fluid neutral ester at tem- J peratures in the range of from about 400 to 500 F.

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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)
  • Engineering & Computer Science (AREA)
  • Combustion & Propulsion (AREA)
  • Lubricants (AREA)

Description

United States Patent 3,290,242 METAL ANTIOXIDANTS FOR FLUOROESTERS Harold Ravner, Accokeek, and Carter 0. Timmons, Oxon to the United States of America as re resented by the Secretary of the Navy v No l rawing. Filed Apr. 18, 1963, Ser. No. 274,064 4 Claims. (Cl. 252-26) Hill, Md., assignors to improvement in the oxidation stability of fluoroesters at high temperatures. I
Developments in military and rndustrial equipment have presented an increasing demand for lubricants and hydraulic fluids which can meet severe operational requirements. Among such requirements is oxidation stability at high temperatures.
Fluid neutral esters of omega-hydroperfluoroalkylcarbinols and saturated aliphatic hydrocarbon polycarboxylic acids have been heretofore suggested as a source of potential high temperature lubricants and hydraullc fluids. As a class these esters lack the necessary oxidation stability which would allow their use as lubricants or as hydraulic fluids at temperatures in the range of about 400 to 500 F. p
It is an object of the present invention to improve the oxidation stability of fluoroesters of the aforesaid class whereby to provide new high temperature lubricants and hydraulic fluids.
We have found certain metals to be antioxidants which impart an exceptional degree of oxidation stability at elevated temperatures in the range of about 400 to 500 F. to fluid neutral esters of omegahydroperfluorolkylcarbinols which have from 5 to 11 carbon atoms and saturated aliphatic hydrocarbon ditriand tetracarboxylic acids which have from 3 to 9 carbon atoms in the hydrocarbon groups.
The metals which we have found to be antioxidants for the fluoroesters of the aforedefined group are barium, tin and zinc. The threshold temperature for antioxidant activity of the metals in the fluoroesters is about 400 F. Below this temperature, the fluoroesters are in themselves oxidation stable. The metals are effective as antioxidants even in small concentrations, as low as on the order of from about 0.05 to 0.5% by weight based on the weight of the fluoroesters, to impart a high order of oxidation stability to the fluoroesters at temperatures in the range of from about 400 to 500 F. The antioxidant metal may be brought into contact with the fluoroesters not only in particle form but also in the form of plates or other larger shapes or configurations as found suitable. The surface of the parts of engines or of other mechanisms with which the fluoroesters come into contact, such as oil lines, may consist of the antioxidant metal or a by-pass system may contain the antioxidant metal in the form of a wire mesh or as a confined mass of grandules through which the fluoroester flows in contact before returning to areas of lubrications.
The mechanism whereby the metals function as antioxidants in the fluoroesters is not known, but is believed to involve the formation of metal ions in the fluoroesters.
The fluid neutral fluoroesters with which the present invention is concerned may be prepared in known way as as described in Ind. Eng. Chem. 48, 445 (1956) from the omega-hydroperfluoroalkylcarbinols of the general formula:
"ice
wherein n is an integer from 2 to 5 and aliphatic polycarboxylic acids of the general formula:
R(COOH) wherein n is an integer from 2 to 4 and R is a saturated aliphatic hydrocarbon group having from 3 to 9 carbon atoms. Thus, the neutral fluoroesters may be derived by the complete esterification of, for example, glutaric, adipic, pimelic, suberic, azelaic, sebacic and undecanedioc acids; methyl succinic, S-methylglutaric, 1,4-dimethyl adipic, 2,2-dimethyladipic, l-methyl-4-ethyl adipic acids, etc.; camphoric acid, tricarballylic acid, butane-1,2,4-tricarboxylic acid, butane 1,1,4-tricarboxylic acid, etc., and butane-1,2,4,4-tetracarboxylic acid, butane-l,l,2,3-tetracarboxylic acid, butane-l,1,2,3-tetracarboxylic acid, etc., with fluoroalcohols of the above general formula which are 1H,1H,'5H-octafluoro-1-pentanol, 1H,lH,7H-dodecafluoro l-pheptanol, 1H,lH,9H-hexadecafluoro-l-nonanol and 1H,lI-I,llH-eicosafluoro-l-undecanol. Illustrative of these fluid neutral fluoroesters are those described in Ind. Eng. Chem. 48, 445, above, for example, bis (1H,lH,5I-I- octafiuoropentyl)- and his (1H,1H,7H-dodecafluoroheptyl) 3-methylglutarates, bis (1H,1H,5H-octafiuoropentyl) adipate and sebacate, tri (1H,1H,5H-octafluoropentyl) tricarballylate, etc.
, temperatures.
The antioxidant activity of the metals for the fluoroesters may be evaluated in terms of increase in the viscosity and rise in the neutralization number of the fluoroesters and the amount of fluoride evolved from the fluoroesters. The lower the value for these factors, the greater in general the oxidation stability imparted to the fluoroesters by the metals at a given temperature in the aforesaid range. Depending upon the conditions of service use, all or less than all of these factors may govern in the selection of the fluoroesters on the basis of oxidation stability. Thus, where the acid developed in the fluoroester is not a corrosion problem, either by virtue of the acid in itself being non-corrosive or the metal parts with which the fluoroester and developed acid come into contact are acid resistant, rise in the neutralization number can be of minor significance. Similarly, evolved fluoride also can be of minor significance where means are provided for venting of the evolved fluoride from an engine or other system in which the fluoroesters are employed.
Increase in viscosity and rise of the neutralization number of the fluoroesters and the amount of fluoride evolved therefrom on heating the fluoroesters to temperature in the aforesaid range in the presence of the metals may be deter-mined by use of the dynamic oxidation test procedure and apparatus described in Ind. Eng. Chem. 39, 491 (1947). In this test, the samples of the fluoroesters with the metal specimen immersed therein are contained in cylindrical cells made of borosilicate glass. The metal specimens, which may be in the form of strips, are used in clean, degreased condition. The control is a like volume of the fluoroester in a cell but without a metal therein. Each of the cells is equipped with a watercooled condenser fitted to the top thereof and has a rubber hose connected from the condenser to a separate water trap. Sealed to the upper wall of each of the cells is a means for delivering bubbled air into the bottom of the fluoroester samples in the cells. The cells containing the fluoroester samples and metal specimens and the cell with the control sample are placed in snugly fitting holesi0.5 F. Clean dry air, free from CO is bubbled through the heated fluoroester samples in the cells at a predetermined volume and rate. The efiluent gases from each of the cells which have passed through the individual associated condenser are led into the water trap provided therefor and the fluoride content of the trap liquid determined by the lead chloro-fluoride method. The amount of evolved fluoride is reported as mg. of fluorine per gram of the fluoroester. The viscosity in centistokes at 100 F. and the neutralization number of the fluoroesters are determined before and after the test. The neutralization number is the number of milligrams of potassium hydroxide required to neutralize the fluoroester.
Indicative of the oxidation stability which can be imparted by the metal antioxidants of the invention to the fluoroesters of the aforesaid group at temperatures in the range of 400 to 500 F. are the results obtained on commercial (Du Pont Company) fluid mixed camphorate esters from the complete esterification with camphoric acid of mixed C C and C fluoroalcohols of the formula H(CF CF CH OH in which the ratio of the fluoroalcohols was approximately 0.5 mole of the C fluoroalcohol, 1 mole of the C fluoroalcohol and 0.5 mole of the C fluoroalcohol. The mixed camphorate fluoroesters had a microboiling point of 351 C. The tests were conducted at 482 F. for 72 hours using 20 ml. samples of the mixed fluoroesters and metal specimens in the fluoroester samples which generally had surface areas of 10 square centimeters. The air was bubbled into the fluoroester samples in the cells at the rate of 1 cc./ gram fluoroester sample/minute. The results of the tests with the several metals as antioxidants are set forth in the following table.
DYNAMIC OXIDATION TEST Viscosity Neutralization Fluoride Metals Increase at N 0. Increase Evolved 100 F. mg. F./gm. (percent) Gelled 36 5. 3 2. 0 Nil 3. 2 0. 45 38 11.0 2. 2
' and not in limitation except as may be defined in the appended claims.
What is claimed is:
1. A composition comprising a fluid neutral ester of a fluoroalcohol of the general formula:
H (CF CF CH OH wherein n is an integer from 2 to 5 and an aliphatic polycarboxylic acid of the general formula:
. wherein n is an integer from 2 to 4 and R is a saturated aliphatic hydrocarbon group having from 3 to 9 carbon atoms and a metal of the group consisting of barium, tin and zinc present therein in amount suflicient to improve the oxidation stability of the fluid neutral ester at tem- J peratures in the range of from about 400 to 500 F.
2. A composition as defined in claim 1, wherein the metal is barium.
3. A composition as defined in claim 1, wherein the metal is tin.
4. A composition as defined in claim 1, wherein the fluid neutral ester is a camphorate of at least one fluoroalcohol of the general formula:
I wherein n is an integer from 2 to 5.
References Cited by the Examiner UNITED STATES PATENTS 4/1956 Reilf 252-56 FOREIGN PATENTS 610,516 12/1960 Canada. 866,053 4/1961 Great Britain.
OTHER REFERENCES Mardles: International Tin Research and Dev. Council, Tech. Publn., Series C #2, pp. 1 to 5 (1934).
Kalichevsky et 211.: Petroleum Refining With Chemicals (1956), Elsevier Pub. Co., p. 590.
Gunderson et al.: Synthetic Lublicants, Reinhold Pub. Co. (1962), p. 189.
DANIEL E. WYMAN, Primary Examiner.
W. H. CANNON, Assistant Examiner.

Claims (1)

1. A COMPOSITION COMPRISING A FLUID NEUTRAL ESTER OF A FLUOROALCOHOL OF THE GENERAL FORMULA:
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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2742427A (en) * 1953-06-08 1956-04-17 Socony Mobil Oil Co Inc Lubricating oil containing dispersed magnesium
CA610516A (en) * 1960-12-13 M. Sturgis Bernard Fluorine containing diesters of camphoric acid
GB866053A (en) * 1956-04-19 1961-04-26 Sinclair Refining Co Lubricants

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA610516A (en) * 1960-12-13 M. Sturgis Bernard Fluorine containing diesters of camphoric acid
US2742427A (en) * 1953-06-08 1956-04-17 Socony Mobil Oil Co Inc Lubricating oil containing dispersed magnesium
GB866053A (en) * 1956-04-19 1961-04-26 Sinclair Refining Co Lubricants

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