WO1991000264A1 - Procede pour la preparation directe sous forme de substance chimique de base a partir de graisses et d'huiles - Google Patents

Procede pour la preparation directe sous forme de substance chimique de base a partir de graisses et d'huiles Download PDF

Info

Publication number
WO1991000264A1
WO1991000264A1 PCT/EP1990/000997 EP9000997W WO9100264A1 WO 1991000264 A1 WO1991000264 A1 WO 1991000264A1 EP 9000997 W EP9000997 W EP 9000997W WO 9100264 A1 WO9100264 A1 WO 9100264A1
Authority
WO
WIPO (PCT)
Prior art keywords
oils
oil
fats
fatty acids
acid amides
Prior art date
Application number
PCT/EP1990/000997
Other languages
German (de)
English (en)
Inventor
Rainer Frische
Jürgen VOLKHEIMER
Klaus Wollmann
Herrmann Schomann
Judith Schneider
Alexander Ach
Renate Gross-Lannert
Bernd Best
Original Assignee
Battelle-Institut E.V.
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
Application filed by Battelle-Institut E.V. filed Critical Battelle-Institut E.V.
Publication of WO1991000264A1 publication Critical patent/WO1991000264A1/fr

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C231/00—Preparation of carboxylic acid amides
    • C07C231/02—Preparation of carboxylic acid amides from carboxylic acids or from esters, anhydrides, or halides thereof by reaction with ammonia or amines

Definitions

  • the invention relates to a process for the production of acid amides of natural fatty acids by direct reaction of raw fats and oils with amide-forming agents.
  • Oils and fats of vegetable and animal origin have always been important raw materials, both for human nutrition and for the production of chemical raw materials used in the manufacture of products for textile finishing, paints, cosmetic preparations, candles, soaps, surfactants, lubricants, Plasticizers, cement and asphalt additives, plastics, and the extraction of free fatty acids.
  • natural fats and oils as renewable raw materials will have an even greater industrial importance in the future.
  • the industrial extraction of chemical raw materials from fats and oils is not without problems.
  • the raw fats and oils to be obtained from oil fruits often contain a large number of disruptive accompanying substances, for example phosphatides, abrasive substances, coloring and odorous substances or hydrocarbons.
  • Such accompanying substances hinder the direct processing of these raw fats and oils. They can act, for example, as catalysts which, particularly in the presence of relatively large amounts of unsaturated fatty acids, cause the starting material to decompose or become resinous, as a result of which the possible yields are greatly reduced.
  • the raw fats and oils have to be pre-cleaned and freed from such ingredients before they can be processed further into chemically usable raw materials by complex methods such as degumming, deacidification, decolorization and deodorization.
  • the oleochemistry which deals with the chemical-technical processing of oils and fats into secondary products, relates Their starting materials are therefore usually pre-cleaned triglycerides from the oil and fat-extracting industry, such as the oil mill industry.
  • the problem arises that the plants of the oil mill industry are designed for processing large quantities of oil fruits, so that the processing of oil fruits, which are only available in small quantities, is hardly possible.
  • oils of newly cultivated oleiferous fruits such as "High oleic” sunflowers or Euphorbia lathyris, which, because of their particular fatty acid pattern, are particularly suitable as starting materials for high-percentage oleic acid, due to the inefficient purification process of being used excluded on an industrial scale.
  • Another disadvantage of some oil fruits is that, in addition to the accompanying substances already mentioned, they often contain nutritionally questionable and even toxic ingredients, so that for this reason their crude oils are used for further processing in plants in which food fats are also obtained and which consequently are cleaned with enormous effort must not be suitable.
  • fats and oils are understood to mean those products of plant or animal origin which essentially consist of mixed glycerol esters of higher fatty acids, ie primarily triglycerides, but which of course also include undetermined quantities of monoglycerides, diglycerides or others in that May contain naturally occurring fatty acid esters.
  • the process is particularly suitable for converting raw fats and oils, as can be obtained by the usual methods, for example by cold or hot pressing with screws or screw presses or by press extraction.
  • Fats and oils are preferably used which have a particularly high content of functional or unusual fatty acids, for example pentaenoic acids, since the corresponding fatty acid derivatives can be obtained particularly easily from these materials with high yield and purity.
  • the proportion of normal functional fatty acids should expediently be at least 50%, the proportion of exceptional fatty acids at least 10%, in each case based on the total number of fatty acid molecules.
  • the oil of Euphorbia lathyris, sunflower oil rich in linoleic or oleic acid, in particular of the "high oleic" type, hardened and unhardened castor oil, linseed oil, rapeseed oil, in particular erucic acid-rich rapeseed oil, the oil of Purgiernut, olive oil or marine oils such as fish oil or walnut oil are particularly preferably used .
  • the solid ingredients that may be present in the starting materials, such as wood or plant residues, are presented appropriately separated from the implementation. The amount of starting material used is arbitrary, so that the process can in principle be carried out both on a laboratory scale and on an industrial scale.
  • the fats and oils are reacted directly with the amide-forming substances.
  • Amide-forming substances can e.g. be: ammonia, formamide or primary and secondary aliphatic, cycloaliphatic, aliphatic-aromatic and aromatic amines, preferably mono- or diamines with 1-44 carbon atoms. This also includes dimeric fatty acids from native fats and oils.
  • the amines can contain further reactive functional groups, e.g. Wear OH groups.
  • additional structural elements or further functional groups e.g., between the two amino functions in the hydrocarbon chain or on the cycloaliphatic or aromatic radical, can Ether groups, amino groups, diamide groups, keto groups or sulfone groups.
  • Preferred amine compounds are methylamine, ethylamine, methylethylamine, dimethylamine, diethylamine, morpholine, benzylamine, naphthylamine, phenylethylamine, aniline, toluidine, 1,2-diaminoethane, 1,3-diaminopropane, 1,6-diaminohexane, 1, 8-diaminooctane, piperazine, 4,7,10-trioxatridecan-l, 13-diamine, 3,3'-diaminodiphenylsulfone, 3,3'-dimethyl-4,4'-diaminodicyclohexylmethane, ethanolamine, 3-aminopropanol and commercially available Ether diamines of the formula
  • n is an integer from 1 to 2000.
  • Particularly preferred compounds are 1,2-diaminoethane and 1,6-diaminohexane.
  • the amines based on the number of amino functions and the fatty acid residues, are preferably used in stoichiometric amounts, but even a slight excess or deficit of amino functions does not significantly influence the reaction yield.
  • the reaction can also be carried out in a suitable solvent in order to ensure a homogeneous reaction.
  • a suitable solvent for example, non-polar solvents, in particular toluene, xylene or petroleum ether, are used.
  • the reaction can take place in a temperature range between 20 and 300 ° C., but a range between 50 and 200 ° C. is preferred, since in this temperature range the reaction times of 1 to 6 hours are not yet too long for the process to be carried out in practice .
  • the reaction is carried out in a closed system, e.g. performed in an autoclave.
  • An inert gas atmosphere such as e.g. Argon or nitrogen or the vapor of an inert solvent is preferred, since this makes it easier to suppress undesirable side reactions such as oxidation of the starting material.
  • catalysts for example ammonium chloride or p-toluenesulfonic acid
  • biological catalysts such as esterases can also be used.
  • other customary auxiliaries and additives such as polymerization inhibitors and antioxidants, for example ascorbic acid or glucose, can be added.
  • the reaction products separate as a precipitate at the latest after the solvent, if any, has been stripped off. They are separated off and then recrystallized from suitable solvents. Both non-polar solvents such as hexane and very polar solvents such as sulfoxides are suitable for this. Is preferably crystallized from methanol or ethanol u.
  • reaction mixture can, however, also be subjected to other cleaning operations, for example a hot steam extraction, the acid amides also being obtained in crystalline form.
  • the oil accompanying substances and the glycerol remain in concentrated form in the mother liquor.
  • Some of these oil accompanying substances, e.g. the vitamins and glycerin that are always present are also of industrial interest. Since the separation of such enriched mixtures is very easy, this process also simplifies the extraction of these substances.
  • the acid amides produced in this way are obtained free from disruptive accompanying substances and with a suitable choice of crude oils with such a high degree of purity that further processing no longer poses any problems.
  • the fatty acid amides - if appropriate also as a mixture - can either be used directly as additives, for example as lubricant additives, or can be converted into other interesting secondary products.
  • Particularly interesting follow-up products that were previously not accessible or could only be obtained with considerable effort are obtained, for example, from difatty acid diamides, which are obtained in the reaction of fats and oils with diamines, in particular from those diamides which are obtained from oils and fats in which a fatty acid which carries a functional group such as a carbon-carbon double bond or an OH group has strong dominance.
  • highly concentrated di oleic acid diamides can be produced from the crude oil of the Euphorbia lathyris seeds using iamines and highly concentrated diricinoleic acid dia iide from crude castor oil.
  • difatty acid diamides can be reacted with suitable bifunctional compounds, for example with diisocyanates, and thus provide novel basic materials for the production of Prepolymers, plastics and plastic additives, for example for adhesives, sealants, plastic foams, lubricants and a large number of other technical auxiliaries.
  • the fatty acid amides can also be used to produce the free fatty acids by the customary processes of saponification, which is less common, particularly with a view to obtaining them Fatty acids such as pentaenoic acids is advantageous. If the fatty acids obtained in this way have functional groups, they can in turn also serve as base materials or additives for plastics.
  • the invention thus not only provides a method by means of which it is possible to process crude oils and fats, which have hitherto not been usable as raw materials, but at the same time it enables the production of a large number of new or previously only with considerable effort available raw materials of great interest for further processing in the chemical industry.
  • Example 1 The invention is explained in more detail by the following examples: Example 1;

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Fats And Perfumes (AREA)

Abstract

Selon un procédé de production d'amides d'acides gras naturels à partir de graisses et d'huiles, le produit de départ est directement mis en réaction avec des réactifs générateurs d'amides.
PCT/EP1990/000997 1989-06-29 1990-06-22 Procede pour la preparation directe sous forme de substance chimique de base a partir de graisses et d'huiles WO1991000264A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE3921343 1989-06-29
DEP3921343.9 1989-06-29

Publications (1)

Publication Number Publication Date
WO1991000264A1 true WO1991000264A1 (fr) 1991-01-10

Family

ID=6383888

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP1990/000997 WO1991000264A1 (fr) 1989-06-29 1990-06-22 Procede pour la preparation directe sous forme de substance chimique de base a partir de graisses et d'huiles

Country Status (4)

Country Link
EP (1) EP0432248A1 (fr)
JP (1) JPH04500686A (fr)
CA (1) CA2019831A1 (fr)
WO (1) WO1991000264A1 (fr)

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB558854A (en) * 1941-06-17 1944-01-25 Nat Oil Prod Co Improvements in or relating to hard wax substitutes
GB632242A (en) * 1946-05-31 1949-11-18 Ici Ltd Improvements in or relating to the manufacture of ricinoleyl amines and to the treatment of water to prevent foaming
GB1084981A (en) * 1963-09-13 1967-09-27 Louis Herbert Libby Improvements in or relating to n-ethyl carboxylic acid amide derivatives
DE1905550A1 (de) * 1968-02-05 1969-10-09 Sumitomo Chemical Co Bis-amide von Fettsaeuren,Verfahren zu ihrer Herstellung und ihre Verwendung zur Herstellung von angereicherten Nahrungsmitteln

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB558854A (en) * 1941-06-17 1944-01-25 Nat Oil Prod Co Improvements in or relating to hard wax substitutes
GB632242A (en) * 1946-05-31 1949-11-18 Ici Ltd Improvements in or relating to the manufacture of ricinoleyl amines and to the treatment of water to prevent foaming
GB1084981A (en) * 1963-09-13 1967-09-27 Louis Herbert Libby Improvements in or relating to n-ethyl carboxylic acid amide derivatives
DE1905550A1 (de) * 1968-02-05 1969-10-09 Sumitomo Chemical Co Bis-amide von Fettsaeuren,Verfahren zu ihrer Herstellung und ihre Verwendung zur Herstellung von angereicherten Nahrungsmitteln

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
CHEMICAL ABSTRACTS, Band 80, Nr. 15, 15. April 1974, (Columbus, Ohio, US), siehe seite 330* Zusammenfassung 82134k, & JP-A-7343089 (Nippon Kasei Co., LTD) 17. Dezember 1973* *

Also Published As

Publication number Publication date
CA2019831A1 (fr) 1990-12-29
EP0432248A1 (fr) 1991-06-19
JPH04500686A (ja) 1992-02-06

Similar Documents

Publication Publication Date Title
DE69816545T2 (de) Herstellung von Materialien mit einem hohen Gehalt an konjugierten Isomeren, die mehrfach ungesättigten Fettsäurereste tragen
DE3446795C2 (de) Verfahren zur Herstellung einer Fettsäuremischung mit einer hohen Konzentration an Eicosapentaensäure
DE2552311C3 (de) Verfahren zur Herstellung von Öl- und Fettfraktionen durch Umestern
EP0433420B1 (fr) Procede de production de diamides d'acides digras symetriques
DE2838488C2 (fr)
WO1992022627A1 (fr) Esters de glycerine d'acides gras a proprietes rheologiques ameliorees
DE3308922A1 (de) Verfahren zur herstellung von fettsaeureestern der ascorbinsaeure
DE10143534B4 (de) Verfahren zur Herstellung von konjugierten Fettsäureestern
EP0542967B1 (fr) Procede de preparation d'un melange de triglycerides depourvu de composants genant son traitement ulterieur
WO1991000264A1 (fr) Procede pour la preparation directe sous forme de substance chimique de base a partir de graisses et d'huiles
DE4203077A1 (de) Verfahren zur herstellung hydroxylierter fettsaeureverbindungen
DE4019089C2 (de) Verfahren zur direkten Gewinnung von Fettsäureamiden aus rohen Fetten und Ölen
EP0728176A1 (fr) Procede de fabrication d'alkylesters inferieurs d'acides gras
EP0583685A1 (fr) Procédé de purification d'amides d'acides gras
EP0150006A1 (fr) Procédé pour la préparation de certaines paires énantiomères de l'ester alpha-cyano-3-phénoxy-4-fluoro-benzylique de l'acide perméthrinique
EP0219601B1 (fr) Procédé de préparation de l'acide (Z)-2-méthyl-2-buténoique
DE1156789B (de) Verfahren zur Umwandlung von Fettsaeureestern einwertiger Alkohole mit isolierten Doppelbindungen (íÀIsolenfettsaeureesterníÂ) in Fettsaeureester mit konjugierten Doppelbindungen (íÀKonjuenfettsaeureesteríÂ)
DD297396A5 (de) Verfahren zur behandlung von fettsaeuren
DE19736737C2 (de) Verfahren zu Herstellung von oxidationsstabilen Oleinen und ihre Verwendung zur Herstellung von Wasch- und Reinigungsmitteln, kosmetischen und/oder pharmazeutischen Formulierungen, ungesättigten Fettalkoholen oder Estern
EP0021433B1 (fr) Procédé de purification de mélanges d'acides ou d'esters gras
DE2253930A1 (de) Verfahren zur herstellung von dicarbonsaeuren
EP1189857A2 (fr) Alcools gras ramifies et largement insatures
AT229288B (de) Verfahren zur Herstellung von Methacrylverbindungen
AT15715B (de) Verfahren zur Herstellung eines Rohmaterials zur Fabrikation von Kerzen, Wachsfarben und Salben.
EP1006175A1 (fr) Oléines stables à l'oxydation

Legal Events

Date Code Title Description
AK Designated states

Kind code of ref document: A1

Designated state(s): JP US

AL Designated countries for regional patents

Kind code of ref document: A1

Designated state(s): AT BE CH DE DK ES FR GB IT LU NL SE

WWE Wipo information: entry into national phase

Ref document number: 1990909729

Country of ref document: EP

WWP Wipo information: published in national office

Ref document number: 1990909729

Country of ref document: EP

WWR Wipo information: refused in national office

Ref document number: 1990909729

Country of ref document: EP

WWW Wipo information: withdrawn in national office

Ref document number: 1990909729

Country of ref document: EP