US2774774A - In situ epoxidation of oleic acid using formic acid - Google Patents

In situ epoxidation of oleic acid using formic acid Download PDF

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US2774774A
US2774774A US419102A US41910254A US2774774A US 2774774 A US2774774 A US 2774774A US 419102 A US419102 A US 419102A US 41910254 A US41910254 A US 41910254A US 2774774 A US2774774 A US 2774774A
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acid
hydrogen peroxide
mole
formic acid
epoxidized
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US419102A
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Frank P Greenspan
Ralph J Gall
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FMC Corp
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FMC Corp
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    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/10—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing oxygen
    • D06M13/11—Compounds containing epoxy groups or precursors thereof
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M7/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made of other substances with subsequent freeing of the treated goods from the treating medium, e.g. swelling, e.g. polyolefins
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M2200/00—Functionality of the treatment composition and/or properties imparted to the textile material
    • D06M2200/40—Reduced friction resistance, lubricant properties; Sizing compositions

Definitions

  • the present invention relates to a method of epoxidizing higher fatty acids containing an ethylenic linkage, and particularly those fatty acids obtained from fatty oils which contain oleic acid.
  • the epoxidation is performed with hydrogen peroxide and formic acid in presence of an organic solvent and at a relatively high'temperature.
  • a similar method of epoxidation but applied particularly to esters of unsaturated higher fatty acids is disclosed in our co-pending application Serial No. 367,752 filed July 13,;1953.
  • Epoxy fatty acids containing oleic acid find application as valuable intermediates in making lubricants, lubricant additives, stabilizers, plasticizers, resins, textile oils, etc.
  • the process described herein has the further advantage of producing as co-product only small amounts of a relatively cleavage resistant formoxy derivative.
  • the desirable end product is one containing the group:
  • HCOH 0a (m or a so-called glycol.
  • an ethylenic unsaturated higher fatty acid that is to say, an acid containing from 16 to 22 carbon atoms, that is an acid obtained from a fatty oil, is reacted, at temperatures between about 50 C. and 100 C. with hydrogen peroxide and formic acid, in the presence of an organic solvent for the acid, for a period of time of from 1 hour to 5 hours.
  • Example 1 100 g. of a commercial fatty acid containing oleic acid together with other unsaturated fatty acids (iodine number 92, equivalent to 0.362 mole of ethylenic unsaturation) were weighed into a three-neck flask equipped with a reflux condenser, thermometer and mechanical stirrer. g. of hexane, and 9.15 g. of formic acid 91% (0.181 mole) were added and the mixture warmed to 60 C. Then 27.06 g.
  • a solvent such as benzene, hexane, and the like
  • Example 2 tained between 60 to 65 C. for an additional 4 hours.
  • the reaction mixture was poured into a separatory funnel and the aqueous layer drawn oil.
  • the oil layer was Washed with Warm water until free of acetic acid.
  • the solvent and traces ofwater were removed in a vacuum stripping column at 60 to 70 C. at a pressure of 5 to millimeters of mercury.
  • the crystallized product obtained was analyzed and found to contain:
  • the method of epoxidizing an ethylenic unsaturated higher fatty acid containing oleic acid which comprises adding to said acid an inert organic solvent and formic acid, warming the mixture to approximately 50 C. to 80 C., then adding aqueous hydrogen peroxide and maintaining the reaction mixture at substantially 50 C. to 80 C. for not more than about 5 hours, said formic acid being present to the extent of 0.25 to 1.0 mole per mole of ethylenic unsaturation to be epoxidized, and said aqueous hydrogen peroxide being present in an amount to provide approximately 1 mole of hydrogen peroxide per mole of ethylenic unsaturation to be epoxidized.
  • the method of epoxidizing oleic acid which comprises adding to said acid an inert organic solvent and formic acid, warming the mixture to approximately 50 C. to 80 C., then adding aqueous hydrogen peroxide and maintaining the reaction mixture at substantially C. to C. for not more than about 5 hours, said formic acid being present to the extent of 0.25 to 1.0 mole per mole of ethylenic unsaturation to be epoxidized, and said aqueous hydrogen peroxide being present in an amount to provide approximately 1 mole of hydrogen peroxide per mole of ethylenic unsaturation to be epoxidized.
  • the method of epoxidizing an ethylenic unsaturated higher fatty acid containing oleic acid which comprises Warming a mixture of said acid, an inert organic solvent, aqueous hydrogen peroxide and formic acid, for not more than five hours, in the temperature range substantially 50 C. to 80 C., said formic acid being present to the extent of 0.25 to 1.0 mole per mole of ethylenic unsaturation to be epoxidized, and said aqueous hydrogen peroxide being present in an amount to provide approximately one mole of hydrogen peroxide per mole of ethylenic unsaturation to be epoxidized.

Description

United States Patent Frank P. Greenspan and Ralph J. Gall, Buffalo, N. Y., assignors, by mesne assignments, to Food Machinery and Chemical Corporation, San Jose, Calif., acorporation of Delaware No Drawing. Application March 26, 1954, Serial No. 419,102
3 Claims. (Cl. 260-3485) The present invention relates to a method of epoxidizing higher fatty acids containing an ethylenic linkage, and particularly those fatty acids obtained from fatty oils which contain oleic acid. The epoxidation is performed with hydrogen peroxide and formic acid in presence of an organic solvent and at a relatively high'temperature. A similar method of epoxidation but applied particularly to esters of unsaturated higher fatty acids is disclosed in our co-pending application Serial No. 367,752 filed July 13,;1953. v
Heretofore, in the principal method of epoxidizing u'nsaturated fatty acids, such as oleic acid, a prepared peracetic acid solution has been employed as the peroxidizing reagent. Such solutions are generally equilibrium mixtures of hydrogen peroxide and peracetic acid with substantial amount of free peroxide present. Under the reaction conditions employed for such epoxidation, substantially only the per-acid fraction of the equilibrium mixture is utilized. There is little or no further formation of peracid from the free peroxide present and this free peroxide is unused; this is extremely wasteful, as much as 20% of the available active oxygen remaining unutilized. Accordingly, reaction techniques, wherein hydrogen peroxide and lower aliphatic acids are caused to react upon the unsaturated fatty acid, have long been sought, for direct epoxidation reactions. Such techniques are standard for hydroxylation reactions with hydrogen peroxide.
Despite the recognized attraction of such an epoxidation procedure, little progress has been made in its fulfillment because of the extreme difliculty of setting up reaction conditions favorable to the required peracid formation from the peroxide and lower aliphatic acid, which simultaneously would not destroy the desired end product, the formed epoxy derivative. It is to be noted that the very same conditions favoring peracid formation from aliphatic acid and hydrogen peroxide, notably high molar ratios of aliphatic acid to H202, high temperatures, high acidity, long reaction times, are known to be deleterious to the survival of .any epoxy compound.
Epoxy fatty acids containing oleic acid find application as valuable intermediates in making lubricants, lubricant additives, stabilizers, plasticizers, resins, textile oils, etc.
The process described herein has the further advantage of producing as co-product only small amounts of a relatively cleavage resistant formoxy derivative.
In epoxidation reactions, therefore, the desirable end product is one containing the group:
-HC-CH o the so-called oxirane group in preference to a hydroxylated precursor of a product of the following structure:
HCOH 0a (m or a so-called glycol.
2,774,774 Patented Dec. 18, 1956 It is an object of the present invention to provide a process for manufacturing epoxidized higher fatty acids by the employment of hydrogen peroxide and formic acid.
It is also an object of the invention to prepare such epoxidized higher fatty acids in extremely short periods of time.
It is a further object of the invention to prepare such epoxidized higher fatty acids without the necessity of employing a prepared performic acid.
It is a further object to provide a process for epoxidation wherein there is economic usage of the oxidizing agent.
It is a further object to provide a safe controllable epoxidation reaction.
In the. broad aspect of the invention an ethylenic unsaturated higher fatty acid, that is to say, an acid containing from 16 to 22 carbon atoms, that is an acid obtained from a fatty oil, is reacted, at temperatures between about 50 C. and 100 C. with hydrogen peroxide and formic acid, in the presence of an organic solvent for the acid, for a period of time of from 1 hour to 5 hours.
The reaction is performed in the presence of a solvent, such as benzene, hexane, and the like, and is continued for a period oftime of from about one-half hour Example 1 100 g. of a commercial fatty acid containing oleic acid together with other unsaturated fatty acids (iodine number 92, equivalent to 0.362 mole of ethylenic unsaturation) were weighed into a three-neck flask equipped with a reflux condenser, thermometer and mechanical stirrer. g. of hexane, and 9.15 g. of formic acid 91% (0.181 mole) were added and the mixture warmed to 60 C. Then 27.06 g. of 50% H202 (0.398 mole) were slowly added over a 40 minute period. The temperature was maintained between 60 to 65 C. for an additional 2 /2 hours. The reaction mixture was poured into a separatory funnel and the aqueous layer drawn off. The oil layer was Washed with warm water until free of formic acid. The solvent and traces of water were removed in a vacuum stripping column at 60 to 70 C. at a pressure of 5 to 10 millimeters of mercury. The crystallized product obtained was analyzed and found to contain:
Percent oxirane oxygen 4.42 (theoretical-6.5%)
Iodine number 5.7
Acid number 183 Example 2 tained between 60 to 65 C. for an additional 4 hours. The reaction mixture was poured into a separatory funnel and the aqueous layer drawn oil. The oil layer was Washed with Warm water until free of acetic acid. The solvent and traces ofwater were removed in a vacuum stripping column at 60 to 70 C. at a pressure of 5 to millimeters of mercury. The crystallized product obtained was analyzed and found to contain:
Percent oxirane oxygen 4.96 (theoretical7.04%) Iodine number 5.5 Acid number 175 What is claimed is:
1. The method of epoxidizing an ethylenic unsaturated higher fatty acid containing oleic acid which comprises adding to said acid an inert organic solvent and formic acid, warming the mixture to approximately 50 C. to 80 C., then adding aqueous hydrogen peroxide and maintaining the reaction mixture at substantially 50 C. to 80 C. for not more than about 5 hours, said formic acid being present to the extent of 0.25 to 1.0 mole per mole of ethylenic unsaturation to be epoxidized, and said aqueous hydrogen peroxide being present in an amount to provide approximately 1 mole of hydrogen peroxide per mole of ethylenic unsaturation to be epoxidized.
2. The method of epoxidizing oleic acid which comprises adding to said acid an inert organic solvent and formic acid, warming the mixture to approximately 50 C. to 80 C., then adding aqueous hydrogen peroxide and maintaining the reaction mixture at substantially C. to C. for not more than about 5 hours, said formic acid being present to the extent of 0.25 to 1.0 mole per mole of ethylenic unsaturation to be epoxidized, and said aqueous hydrogen peroxide being present in an amount to provide approximately 1 mole of hydrogen peroxide per mole of ethylenic unsaturation to be epoxidized.
3. The method of epoxidizing an ethylenic unsaturated higher fatty acid containing oleic acid which comprises Warming a mixture of said acid, an inert organic solvent, aqueous hydrogen peroxide and formic acid, for not more than five hours, in the temperature range substantially 50 C. to 80 C., said formic acid being present to the extent of 0.25 to 1.0 mole per mole of ethylenic unsaturation to be epoxidized, and said aqueous hydrogen peroxide being present in an amount to provide approximately one mole of hydrogen peroxide per mole of ethylenic unsaturation to be epoxidized.
Swern: JACS 67:1786-89 (1945). MacArdle: Use of Solvents, pp. l-3, Van Nostrand Co., N. Y. (1925).

Claims (1)

1. THE METHOD OF EXPOXIDIZING AN ETHYLENIC UNSATURATED HIGHER FATTY ACID CONTAINING OLEIC ACID WHICH COMPRISES ADDING TO SAID ACID AN INERT ORGANIC SOLVENT AND FORMIC ACID, WARMING THE MIXTURE TO APPROXIMATELY 50* C. TO 80* C., THEN ADDING AQUEOUS HYDROGEN PEROXIDE AND MAINTAINING THE REACTION MIXTURE AT SUBSTANTIALLY 50* C. TO 80* C. FOR NOT MORE THAN ABOUT 5 HOURS, SAID FORMIC ACID BAING PRESENT TO THE EXTENT OF 0.25 TO 1.0 MOLE PER MOLE OF ETHYLENIC UNSATURATION TO BE EPOXIDIZED, AND SAID AQUEOUS HYDROGEN PEROXIDE BEING PRESENT IN AN AMOUNT TO PROVIDE APPROXIMATELY 1 MOLE OF HYDROGEN PEROXIDE PER MOLE OF ETHYLENIC UNSATURATION TO BE EPOXIDIZED.
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Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2903465A (en) * 1959-09-08 Epoxidation
US2992237A (en) * 1961-07-11 Process for the production of com-
US3360531A (en) * 1964-10-06 1967-12-26 Ashland Oil Inc In situ epoxidation process
EP0032989B1 (en) * 1980-01-26 1983-02-16 Degussa Aktiengesellschaft Process for preparing alpha epoxides containing from 11 to 24 carbon atoms
EP0151402A2 (en) * 1984-01-23 1985-08-14 Henkel Kommanditgesellschaft auf Aktien Composition for the melt spinning of synthetic fibrous materials
EP0303066A2 (en) * 1987-07-24 1989-02-15 Henkel Kommanditgesellschaft auf Aktien Lubricant for the manufacture of synthetic yarns and filaments
WO1996011919A1 (en) * 1994-10-14 1996-04-25 Henkel Kommanditgesellschaft Auf Aktien Process for preparing epoxide group-containing organic compounds
US20050159608A1 (en) * 2004-01-20 2005-07-21 Turner Robert B. Method of preparing an epoxidized functional vegetable oil
US20080125569A1 (en) * 2004-10-26 2008-05-29 Wehmeyer Richard M Method for Alkoxylating Active Hydrogen Containing Compounds and the Alkoxylated Compounds Made Therefrom

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2485160A (en) * 1948-10-23 1949-10-18 Rohm & Haas Process for the epoxidation of esters of oleic and linoleic acids
US2567930A (en) * 1945-01-30 1951-09-18 Thomas W Findley Preparation of epoxy compounds by oxidation of cis-monoolefine compounds

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2567930A (en) * 1945-01-30 1951-09-18 Thomas W Findley Preparation of epoxy compounds by oxidation of cis-monoolefine compounds
US2485160A (en) * 1948-10-23 1949-10-18 Rohm & Haas Process for the epoxidation of esters of oleic and linoleic acids

Cited By (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2903465A (en) * 1959-09-08 Epoxidation
US2992237A (en) * 1961-07-11 Process for the production of com-
US3360531A (en) * 1964-10-06 1967-12-26 Ashland Oil Inc In situ epoxidation process
EP0032989B1 (en) * 1980-01-26 1983-02-16 Degussa Aktiengesellschaft Process for preparing alpha epoxides containing from 11 to 24 carbon atoms
TR22796A (en) * 1984-01-23 1988-07-19 Henkel Kgaa THREADED SYNTHETIC FIBER MATERIAL THROUGH THREADED DRAWING JACKET SPECIAL YARN DRAWING PREPARATE
EP0151402A3 (en) * 1984-01-23 1988-03-23 Henkel Kommanditgesellschaft Auf Aktien Composition for the melt spinning of synthetic fibrous materials
EP0151402A2 (en) * 1984-01-23 1985-08-14 Henkel Kommanditgesellschaft auf Aktien Composition for the melt spinning of synthetic fibrous materials
US4871592A (en) * 1984-01-23 1989-10-03 Henkel Kommanditgesellschaft Auf Aktien Spinning preparations for melt spinning synthetic fibers
EP0303066A2 (en) * 1987-07-24 1989-02-15 Henkel Kommanditgesellschaft auf Aktien Lubricant for the manufacture of synthetic yarns and filaments
EP0303066A3 (en) * 1987-07-24 1990-11-07 Henkel Kommanditgesellschaft auf Aktien Lubricant for the manufacture of synthetic yarns and filaments
WO1996011919A1 (en) * 1994-10-14 1996-04-25 Henkel Kommanditgesellschaft Auf Aktien Process for preparing epoxide group-containing organic compounds
US20050159608A1 (en) * 2004-01-20 2005-07-21 Turner Robert B. Method of preparing an epoxidized functional vegetable oil
WO2005072178A2 (en) * 2004-01-20 2005-08-11 Biobase Chemical Method for preparing an epoxidized functional vegetable oil
WO2005072178A3 (en) * 2004-01-20 2006-11-02 Biobase Chemical Method for preparing an epoxidized functional vegetable oil
US20080125569A1 (en) * 2004-10-26 2008-05-29 Wehmeyer Richard M Method for Alkoxylating Active Hydrogen Containing Compounds and the Alkoxylated Compounds Made Therefrom

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