EP0437592A1 - Process for preparing plastics from raw fats and oils - Google Patents

Process for preparing plastics from raw fats and oils

Info

Publication number
EP0437592A1
EP0437592A1 EP19900912681 EP90912681A EP0437592A1 EP 0437592 A1 EP0437592 A1 EP 0437592A1 EP 19900912681 EP19900912681 EP 19900912681 EP 90912681 A EP90912681 A EP 90912681A EP 0437592 A1 EP0437592 A1 EP 0437592A1
Authority
EP
European Patent Office
Prior art keywords
oils
fats
acid
compounds
plastics
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.)
Withdrawn
Application number
EP19900912681
Other languages
German (de)
French (fr)
Inventor
Rainer Frische
Jürgen VOLKHEIMER
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.)
Battelle Institut eV
Original Assignee
Battelle Institut eV
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Filing date
Publication date
Application filed by Battelle Institut eV filed Critical Battelle Institut eV
Publication of EP0437592A1 publication Critical patent/EP0437592A1/en
Withdrawn legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/02—Polycondensates containing more than one epoxy group per molecule
    • C08G59/027—Polycondensates containing more than one epoxy group per molecule obtained by epoxidation of unsaturated precursor, e.g. polymer or monomer
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D303/00—Compounds containing three-membered rings having one oxygen atom as the only ring hetero atom
    • C07D303/02—Compounds containing oxirane rings
    • C07D303/38—Compounds containing oxirane rings with hydrocarbon radicals, substituted by carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals
    • C07D303/40—Compounds containing oxirane rings with hydrocarbon radicals, substituted by carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals by ester radicals
    • C07D303/42—Acyclic compounds having a chain of seven or more carbon atoms, e.g. epoxidised fats
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/36—Hydroxylated esters of higher fatty acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/50—Amines
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/62—Alcohols or phenols

Definitions

  • the present invention relates to a method for producing plastic additives and plastics from raw fats and oils.
  • Fats and oils are used not only for human nutrition, but also as a starting material for the production of a large number of technically important raw materials. Under certain conditions and to a very limited extent, fats and oils can also be used as the starting material for the production of polymers and plastics.
  • Natural fats and oils which contain hydroxy fatty acid triglycerides and their derivatives are particularly suitable for the production of technically usable products, in particular polymers and plastics.
  • thermosetting plastics are preferably obtained.
  • Suitable for such reactions are, for example, castor oil or hydrogenated castor oil, which can be used directly as triglycerides.
  • the scope of this method is severely limited by the number of oils and fats containing hydroxyl groups available.
  • a further disadvantage is that the oils and fats have to be cleaned before the reaction in order to free them from disruptive accompanying substances, in particular from undesired coloring components.
  • the object of the present invention was therefore to provide a method which is independent of complex and lossy cleaning methods, and with the aid thereof greases and oils with little industrial importance can be made accessible as starting material for the production of plastics and plastic comonomers.
  • the present invention accordingly relates to a process for producing plastic comonomers and plastics from fats and oils of unsaturated fatty acids, which is characterized as in claim 1.
  • all raw fats and oils in which glycerides of unsaturated fatty acids occur can be used for the process according to the invention.
  • fats and oils are expediently used in which the proportion of unsaturated fatty acid residues, based on the total number of fatty acids, is known and is at least 50%. Preference is given here to oils in which the fatty acid residues each have only a single double bond.
  • the oil of Euphorbia lathyris and the oils of oleic acid-rich sunflowers, in particular of the "high oleic" type are particularly preferably used.
  • the raw fats and oils are obtained by the usual methods, for example by cold or hot pressing with screw or screw presses or by press extractions, and can be used directly after the removal of any solid ingredients, such as wood or plant residues.
  • the raw fats and oils are in a suitable solvent such as e.g. Formic acid or acetic acid with performic acids or peracetic acid, advantageously reacted at temperatures between -5 and 80 ° C to oxidized triglycerides.
  • a suitable solvent such as e.g. Formic acid or acetic acid with performic acids or peracetic acid
  • the reaction takes place according to a mechanism in which the epoxy is initially formed upon reaction of the double bond of the fatty acid residue, which is then cleaved at higher temperatures to form a diol.
  • a suitable solvent such as e.g. Formic acid or acetic acid with performic acids or peracetic acid
  • the amount of peracids used depends on how strongly unsaturated the starting triglyceride is and what degree of oxidation is desired. Underdosing can be desirable, particularly in the case of highly unsaturated triglycerides, since this can have a targeted influence on the number of oxidized groups. It is advantageous here that the destruction of the accompanying substances always precedes the oxidation of the triglycerides, so that even in the event of partial oxidation of the double formations, no disruptive coloring components remain in the reaction mixture.
  • the fats and oils can also be oxidized by dropwise dissolving the triglyceride in acetic acid or formic acid, advantageously in the form of a commercially available 30% solution is added.
  • the peric acid is formed by reaction of the solvent with the hydrogen peroxide and then continues to react with the fats and oils to be oxidized.
  • the resulting oxidation product can be isolated in high yield as a water-clear or colorless, viscous solution.
  • the oxidized triglycerides are thus available in a form in which they can be used directly, i.e. without further purification steps. can only be used after removal of excess peracid, water and solvent.
  • crosslinking agents or as comonomers for example in the classic polyester and polyurethane plastic systems - they change the properties of the plastic and are therefore an inexpensive substitute for castor oil, which in its pure form is very expensive and cannot be used as a press oil.
  • the diols can be partially replaced by oxidized triglycerides before the reaction with diisocyanates.
  • the result is polymers which contain both the diols and the oxidized triglycerides linked via urethane groups.
  • the oxidized fats and oils can be transposed directly with bi- or multifunctional compounds which are able to react with hydroxyl groups or epoxy groups. implement annuity polymers and plastics.
  • the percentage of triglyceride molecules which do not contain at least one unsaturated fatty acid residue is relatively low. For this reason, most trigylceride molecules contain at least two OH groups when fully oxidized.
  • Such oxidized fats and oils react almost completely, including the total mass of the triglycerides. Since the oxidation according to the invention does not in principle lead to cleavage of the unsaturated fatty acids, the total mass of the fats can be converted into polymers, which represents a significant advance over the processes available according to the prior art.
  • Bi- or multifunctional compounds which are suitable for reaction with triglycerides containing hydroxyl groups are, for example, di- or polyisocyanates as are known in plastics production. Hexamethylene diisocyanate and methylene diphenylene diisocyanate (MDI) are preferably used.
  • MDI methylene diphenylene diisocyanate
  • Other suitable bifunctional compounds are dicarboxylic acids and their active derivatives, e.g. Acid chlorides, esters and anhydrides.
  • bifunctional compounds which are preferably used are phthalic acid dichloride, adipic acid dichloride, maleic acid dichloride and phosgene.
  • the triglycerides are linked to one another either via urethane or via ester bonds.
  • Triglycerides containing epoxy groups can be linked together, for example, with diols, diamines and amino alcohols.
  • diamines or amino alcohols are primary and secondary aliphatic, cycloaliphatic, aliphatic-aromatic and aromatic diamines or amino alcohols, preferably having 2 to 44 carbon atoms. These also include amines from dimeric fatty acids. Between the two amino functions of the diamines, there may be additional structural elements or further functional groups, for example ether groups, diamide groups, amino groups, keto groups or sulfone groups, in the hydrocarbon chain or on the cycloaliphatic or aromatic radical.
  • Diamines used with preference are 1,2-diaminoethane, 1,3-diaminopropane, 1,6-diaminohexane, 1,8-diaminooctane, piperazine, diethylenetriamine, 4,7,10-trioxatridecane-l, 13-diamine, 3,3 ' -Diaminodiphenylsulfone, 3,3'-dimethyl-4 r 4 -diaminodicyclohexylmethane and commercially available ether diamines of the formula
  • n can be an integer from 1 to about 2000.
  • 1,2-Diaminoethane and 1,6-diaminohexane are particularly preferably used.
  • Preferred amino alcohols are 2-aminoethanol and 3-aminopropanol.
  • Suitable diols for the reaction are primary and secondary aliphatic, cycloaliphatic, aliphatic-aromatic and aromatic diols, preferably having 2 to 44 carbon atoms.
  • Glycol, 1,4-butanediol, 2-butyne-1,4-diol, 2-butene-1,4-diol, 1,5-pentanediol, 1,6-hexanediol, 1,10-decanediol, neopentyl glycol are preferably used , N, N-diethylamino-propanediol-2,3 or hydroxypivalic acid neopentyl glycol ester.
  • 1,4-Butanediol and 1,10-decanediol are particularly preferred.
  • the reaction components are expediently carried out in a temperature range between 20 and 200.degree.
  • the catalysts and stabilizers customary in plastics production can be added to the reaction mixture.
  • the reaction can take place in solution or in the melt. It is expedient to work under an inert gas atmosphere.
  • the plastics obtainable by the process according to the invention are transparent and thermoset. Their properties essentially depend on the type of starting oils and fats, the degree of oxidation and crosslinking, as well as the type of bi- or multifunctional compounds and their molar mixing ratio to the oxidized triglycerides. In general, the general rules of classic polymer chemistry must also be taken into account here.
  • the amount of bi- or multifunctional compound is preferably selected so that the proportion of the reactive groups of these compounds, based on the hydroxyl or epoxy groups in the triglyceride, is between 0.5 and 1.5.
  • the properties of the plastics can be varied particularly easily, because here the mixing ratio of oxidized triglycerides leading to polymers is to be bi- or multifunctional connection is particularly wide.
  • the number of hydroxyl groups also increases the hydrophilicity and adsorptivity, ie the ability of the plastic to attach to other substances such as glass, lacquers and metals.
  • the method according to the invention has now made it possible to also make fats and oils accessible for plastic processing which previously could not be used because of their disruptive accompanying substances.
  • the present invention enables not only simple but also inexpensive provision of technically useful products and intermediate products.

Abstract

Dans un procédé pour fabriquer des comonomères de plastique et des plastiques à partir de graisses et d'huiles contenant des acides gras insaturés, des graisses et des huiles brutes insaturées sont oxydées avec de l'acide performique ou de l'acide peracétique pour donner des composés d'époxy ou d'hydroxy. Pour fabriquer des plastiques, ces composés d'époxy ou d'hydroxy sont ensuite convertis en polymères avec des composés bi- ou multifonctionnels capables de réagir avec des groupes époxy ou hydroxy.In a process for making plastic comonomers and plastics from fats and oils containing unsaturated fatty acids, unsaturated crude fats and oils are oxidized with performic acid or peracetic acid to give epoxy or hydroxy compounds. To make plastics, these epoxy or hydroxy compounds are then converted to polymers with bi- or multifunctional compounds capable of reacting with epoxy or hydroxy groups.

Description

Verfahren zur Herstellung von Kunststoffen aus rohen Fetten und ÖlenProcess for the production of plastics from raw fats and oils
Die vorliegende Erfindung bezieht sich auf ein Verfahren zur Herstellung von Kunststoffadditiven und Kunststoffen aus rohen Fetten und Ölen.The present invention relates to a method for producing plastic additives and plastics from raw fats and oils.
Fette und Öle dienen nicht nur der menschlichen Ernährung, sondern auch als Ausgangs aterial zur Erzeugung einer Vielzahl technisch wichtiger Grundstoffe. Unter bestimmten Voraussetzun¬ gen und in bisher sehr beschränktem Maß können Fette und Öle auch als Ausgangsmaterial zur Erzeugung von Polymeren und Kunst¬ stoffen herangezogen werden.Fats and oils are used not only for human nutrition, but also as a starting material for the production of a large number of technically important raw materials. Under certain conditions and to a very limited extent, fats and oils can also be used as the starting material for the production of polymers and plastics.
Natürliche Fette und Öle, die Hydroxyfettsäuretriglyceride und ihre Derivate enthalten, sind für die Erzeugung von technisch nutzbaren Produkten, insbesondere von Polymeren und Kunststof¬ fen, besonders geeignet. So ist es beispielsweise möglich, bestimmte öle und Fette, die in überwiegendem Maße zwei oder mehr Alkoholgruppen pro Triglyceridmolekül enthalten, durch Umsetzung mit entsprechenden reaktiven Verbindungen, z.B. mit Diisocyanaten, über diese Hydroxygruppen zu polymeren Strukturen zu verarbeiten. Man erhält so vorzugsweise duroplastische Kunst¬ stoffe. Geeignet für derartige Umsetzungen sind beispielsweise Ricinusöl oder hydriertes Ricinusöl, die direkt als Triglyceride eingesetzt werden können. Die Anwendungsbreite dieser Methode wird allerdings durch die Anzahl der zur Verfügung stehenden hydroxylgruppen-haltigen Öle und Fette stark eingeschränkt. Ein weiterer Nachteil ist es, daß die Öle und Fette vor der Umset¬ zung gereinigt werden müssen, um sie von störenden Begleitstof- fen, insbesondere von unerwünschten farbgebenden Komponenten, zu befreien.Natural fats and oils which contain hydroxy fatty acid triglycerides and their derivatives are particularly suitable for the production of technically usable products, in particular polymers and plastics. For example, it is possible to remove certain oils and fats, which predominantly contain two or more alcohol groups per triglyceride molecule, by reaction with corresponding reactive compounds, e.g. with diisocyanates to be processed into polymeric structures via these hydroxyl groups. In this way, thermosetting plastics are preferably obtained. Suitable for such reactions are, for example, castor oil or hydrogenated castor oil, which can be used directly as triglycerides. However, the scope of this method is severely limited by the number of oils and fats containing hydroxyl groups available. A further disadvantage is that the oils and fats have to be cleaned before the reaction in order to free them from disruptive accompanying substances, in particular from undesired coloring components.
Aufgabe der vorliegenden Erfindung war es daher, ein Verfahren zur Verfügung zu stellen, das unabhängig von aufwendigen und verlustreichen Reinigungsverfahren ist, und mit dessen Hilfe auch Fette und Öle mit bislang geringer industrieller Bedeutung als Ausgangsmaterial für die Herstellung von Kunststoffen und Kunststoffcomonomeren zugänglich gemacht werden können.The object of the present invention was therefore to provide a method which is independent of complex and lossy cleaning methods, and with the aid thereof greases and oils with little industrial importance can be made accessible as starting material for the production of plastics and plastic comonomers.
Gegenstand der vorliegenden Erfindung ist demnach ein Verfahren zur Herstellung von Kunststoffcomonomeren und Kunststoffen aus Fetten und Ölen ungesättigter Fettsäuren, das wie in Anspruch 1 gekennzeichnet ist.The present invention accordingly relates to a process for producing plastic comonomers and plastics from fats and oils of unsaturated fatty acids, which is characterized as in claim 1.
Wie bekannt, lassen sich reine ungesättigte Fettsäuren oder deren Derivate durch Umsetzung mit organischen Persäuren zu Epoxidverbindungen oder Hydroxyverbindungen umsetzen. Überra¬ schend wurde nunmehr gefunden, daß sich auch ungereinigte Triglyceride, wie sie rohe Fette und öle darstellen, auf diese Weise problemlos oxidieren lassen, ohne daß die im Ausgangsmate¬ rial stets vorhandenen Begleitstoffe vorher entfernt werden müssen. Als weiterer unerwarteter Effekt kommt hinzu, daß gerade die für die Qualität der Folgeprodukte so nachteiligen und daher für die weitere Umsetzung unerwünschten Färb- und Geruchsstoffe bei dieser Reaktion vollständig zerstört werden, so daß man nach dieser Methode vollkommen farblose Reaktionsprodukte erhalten kann.As is known, pure unsaturated fatty acids or their derivatives can be converted into epoxy compounds or hydroxy compounds by reaction with organic peracids. Surprisingly, it has now been found that even unpurified triglycerides such as raw fats and oils can easily be oxidized in this way without the accompanying substances which are always present in the starting material having to be removed beforehand. Another unexpected effect is that the colorants and odorants which are so disadvantageous for the quality of the secondary products and therefore undesirable for the further implementation are completely destroyed in this reaction, so that completely colorless reaction products can be obtained by this method.
Für das erfindungsgemäße Verfahren können grundsätzlich sämtli¬ che rohen Fette und Öle eingesetzt werden, in denen Glyceride ungesättigter Fettsäuren vorkommen. Zweckmäßig werden jedoch Fette und Öle eingesetzt, in denen der Anteil an ungesättigten Fettsäureresten, bezogen auf die Gesamtzahl von Fettsäuren bekannt ist und wenigstens 50 % beträgt. Bevorzugt werden hier¬ bei Öle, in denen die Fettsäurereste nur jeweils eine einzige Doppelbindung aufweisen. Besonders bevorzugt werden das Öl der Euphorbia lathyris und die Öle ölsäurereicher Sonnenblumen, insbesondere der Art "High oleic" eingesetzt. Die rohen Fette und Öle werden nach den üblichen Methoden, z.B. durch Kalt- oder Heißpressen mit Schnecken- oder Spindelpressen oder durch Preßextraktionen, gewonnen und können nach Abtrennung eventuell vorhandener fester Inhaltsstoffe wie Holz- oder Pflan¬ zenreste direkt verwendet werden.In principle, all raw fats and oils in which glycerides of unsaturated fatty acids occur can be used for the process according to the invention. However, fats and oils are expediently used in which the proportion of unsaturated fatty acid residues, based on the total number of fatty acids, is known and is at least 50%. Preference is given here to oils in which the fatty acid residues each have only a single double bond. The oil of Euphorbia lathyris and the oils of oleic acid-rich sunflowers, in particular of the "high oleic" type, are particularly preferably used. The raw fats and oils are obtained by the usual methods, for example by cold or hot pressing with screw or screw presses or by press extractions, and can be used directly after the removal of any solid ingredients, such as wood or plant residues.
Erfindungsgemäß werden die rohen Fette und Öle in einem geeigne¬ ten Lösungsmittel wie z.B. Ameisensäure oder Essigsäure mit Perameisensäuren oder Peressigsäure, zweckmäßig bei Temperaturen zwischen -5 und 80°C zu oxidierten Triglyceriden umgesetzt. Die Umsetzung erfolgt nach einem Mechanismus, bei dem unter Reaktion der Doppelbindung des Fettsäurerestes zunächst das Epoxid ent¬ steht, das dann bei höheren Temperaturen unter Bildung eines Diols gespalten wird. Bei niedrigen Temperaturen von etwa -5 bis +20°C und kurzen Reaktionszeiten bilden sich entsprechend in erster Linie Epoxide, im Temperaturbereich zwischen +20 und 80°C und bei längeren Reaktionszeiten erhält man vorzugsweise Diole bzw. im Falle mehrerer Doppelbindungen Polyole. Die Menge der eingesetzten Persäuren richtet sich danach, wie stark ungesät¬ tigt das Ausgangstriglycerid ist und welcher Grad der Oxidation gewünscht wird. Unterdosierungen können - insbesondere bei hoch ungesättigten Triglyceriden - durchaus erwünscht sein, da da¬ durch gezielt Einfluß auf die Anzahl der oxidierten Gruppen genommen werden kann. Hierbei ist es von Vorteil, daß die Zer¬ störung der Begleitstoffe der Oxidation der Triglyceride immer vorausgeht, so daß selbst bei partieller Oxidation der Doppel¬ bildungen keine störenden farbgebenden Komponenten mehr in der Reaktionsmischung zurückbleiben.According to the invention, the raw fats and oils are in a suitable solvent such as e.g. Formic acid or acetic acid with performic acids or peracetic acid, advantageously reacted at temperatures between -5 and 80 ° C to oxidized triglycerides. The reaction takes place according to a mechanism in which the epoxy is initially formed upon reaction of the double bond of the fatty acid residue, which is then cleaved at higher temperatures to form a diol. At low temperatures of about -5 to + 20 ° C and short reaction times, primarily epoxides are formed accordingly, in the temperature range between +20 and 80 ° C and at longer reaction times, preference is given to diols or, in the case of two double bonds, polyols. The amount of peracids used depends on how strongly unsaturated the starting triglyceride is and what degree of oxidation is desired. Underdosing can be desirable, particularly in the case of highly unsaturated triglycerides, since this can have a targeted influence on the number of oxidized groups. It is advantageous here that the destruction of the accompanying substances always precedes the oxidation of the triglycerides, so that even in the event of partial oxidation of the double formations, no disruptive coloring components remain in the reaction mixture.
Anstelle der direkten Zugabe der Persäuren kann die Oxidation der Fette und Öle auch dadurch erfolgen, daß der Lösung des Triglycerids in Essigsäure oder Ameisensäure tropfenweise Was¬ serstoffperoxid, zweckmäßig in Form einer handelsüblichen 30%igen Lösung, hinzugefügt wird. Hierbei bildet sich die Per- εäure durch Reaktion des Lösungsmittels mit dem Wasserstoffper¬ oxid und reagiert dann weiter mit den zu oxidierenden Fetten und Ölen.Instead of the direct addition of the peracids, the fats and oils can also be oxidized by dropwise dissolving the triglyceride in acetic acid or formic acid, advantageously in the form of a commercially available 30% solution is added. The peric acid is formed by reaction of the solvent with the hydrogen peroxide and then continues to react with the fats and oils to be oxidized.
Nach Beendigung der Reaktion wird ein möglicher Überschuß an Persäure bzw. Wasserstoffperoxid in üblicher Weise entfernt, z.B. durch Katalysatoren oder Reduktionsmittel. Anschließend werden Wasser und Lösungsmittel im Vakuum weitestgehend aus dem Reaktionsgemisch entfernt.After the reaction has ended, a possible excess of peracid or hydrogen peroxide is removed in a conventional manner, e.g. through catalysts or reducing agents. Then water and solvent are largely removed from the reaction mixture in vacuo.
Da bei der Oxidation der rohen Fette und Öle sämtliche beglei¬ tenden Farbstoffe zerstört werden, kann das resultierende Oxida- tionsprodukt in hoher Ausbeute als wasserklare bzw. farblose, viskose Lösung isoliert werden. Die oxidierten Triglyceride stehen somit in einer Form zur Verfügung, in der sie ohne weite¬ re Reinigungsschritte direkt, d.h. lediglich nach Entfernung von überschüssiger Persäure, Wasser und Lösungsmittel, weiterver¬ wendet werden können. Als Vernetzungsmittel oder als Comonome- re - beispielsweise in den klassischen Polyester- und Polyuret- han-Kunststoffsystemen - verändern sie die Kunststoffeigenεchaf- ten und sind daher ein kostengünstiges Substitutionsmittel für Ricinusöl, das in reiner Form sehr teuer und als Preßöl nicht einsetzbar ist. Beispielsweise lassen sich bei Polyurethankunst¬ stoffen aus Diolen und Diisocyanaten die Diole teilweise durch oxidierte Triglyceride vor der Umsetzung mit Diisocyanaten ersetzen. Es entstehen dann Polymere, die sowohl die Diole wie die oxidierten Triglyceride über Urethangruppen verknüpft ent¬ halten.Since all accompanying dyes are destroyed during the oxidation of the raw fats and oils, the resulting oxidation product can be isolated in high yield as a water-clear or colorless, viscous solution. The oxidized triglycerides are thus available in a form in which they can be used directly, i.e. without further purification steps. can only be used after removal of excess peracid, water and solvent. As crosslinking agents or as comonomers - for example in the classic polyester and polyurethane plastic systems - they change the properties of the plastic and are therefore an inexpensive substitute for castor oil, which in its pure form is very expensive and cannot be used as a press oil. For example, in the case of polyurethane plastics made from diols and diisocyanates, the diols can be partially replaced by oxidized triglycerides before the reaction with diisocyanates. The result is polymers which contain both the diols and the oxidized triglycerides linked via urethane groups.
Weiterhin lassen sich die oxidierten Fette und öle direkt mit bi- oder multifunktionellen Verbindungen, die zur Reaktion mit Hydroxygruppen oder Epoxygruppen in der Lage sind, zu transpa- renten Polymeren und Kunststoffen umsetzen. Bei Einsatz von Fetten und ölen, in denen der Anteil an ungesättigten Fettsäuren um 50 % beträgt, wie beispielsweise beim Talg mit ca. 50 % Ölsäure im Fettsäuremuster, ist der Prozentsatz an Triglycerid- molekülen, die nicht wenigstens einen ungesättigten Fettsäure- rest enthalten, relativ gering. Aus diesem Grund enthalten die meisten Trigylcerid oleküle bei vollständiger Oxidation minde¬ stens zwei OH-Gruppen. Solche oxidierten Fette und Öle reagieren praktisch vollständig unter Einbindung der Gesamtmasse der Triglyceride. Da die erfindungsgemäße Oxidation grundsätzlich zu keiner Spaltung der ungesättigten Fettsäuren führt, kann die Gesamtmasse der Fette zu Polymeren umgesetzt werden, was einen deutlichen Fortschritt gegenüber den bisherigen nach dem Stand der Technik verfügbaren Verfahren darstellt.Furthermore, the oxidized fats and oils can be transposed directly with bi- or multifunctional compounds which are able to react with hydroxyl groups or epoxy groups. implement annuity polymers and plastics. When using fats and oils in which the proportion of unsaturated fatty acids is around 50%, such as in the case of tallow with approx. 50% oleic acid in the fatty acid pattern, the percentage of triglyceride molecules which do not contain at least one unsaturated fatty acid residue is relatively low. For this reason, most trigylceride molecules contain at least two OH groups when fully oxidized. Such oxidized fats and oils react almost completely, including the total mass of the triglycerides. Since the oxidation according to the invention does not in principle lead to cleavage of the unsaturated fatty acids, the total mass of the fats can be converted into polymers, which represents a significant advance over the processes available according to the prior art.
Bi- oder multifunktionelle Verbindungen, die sich für die Umset¬ zung mit hydroxylgruppenhaltigen Triglyceriden eignen, sind beispielsweise Di- oder Polyisocyanate, wie sie in der Kunst¬ stoffherstellung bekannt sind. Bevorzugt eingesetzt werden Hexamethylendiisocyanat und Methylendiphenylendiisocyanat (MDI). Auch die Di- oder Polyisocyanate der Desmodur-Klasse, wie sie beispielsweise unter den Handelsnamen Des odur E14 bzw. T80 erhältlich sind, können problemlos verwendet werden. Andere geeignete bifunktionelle Verbindungen sind Dicarbonsäuren und deren aktive Derivate, z.B. Säurechloride, Ester und Anhydride. Bevorzugt eingesetzte Vertreter dieser Art bifunktioneller Ver¬ bindungen sind Phthalsäuredichlorid, Adipinsäuredichlorid, Maleinsäuredichlorid und Phosgen. Bei Einsatz der genannten Verbindungen werden die Triglyceride entweder über Urethan- oder über Esterbindungen miteinander verknüpft.Bi- or multifunctional compounds which are suitable for reaction with triglycerides containing hydroxyl groups are, for example, di- or polyisocyanates as are known in plastics production. Hexamethylene diisocyanate and methylene diphenylene diisocyanate (MDI) are preferably used. The di- or polyisocyanates of the Desmodur class, as are available, for example, under the trade names Des odur E14 or T80, can also be used without any problems. Other suitable bifunctional compounds are dicarboxylic acids and their active derivatives, e.g. Acid chlorides, esters and anhydrides. Representatives of this type of bifunctional compounds which are preferably used are phthalic acid dichloride, adipic acid dichloride, maleic acid dichloride and phosgene. When using the compounds mentioned, the triglycerides are linked to one another either via urethane or via ester bonds.
Epoxygruppenhaltige Triglyceride können z.B. mit Diolen, Diami¬ nen und A inoalkoholen miteinander verknüpft werden. Als Diamine oder Aminoalkohole eignen sich primäre and sekundäre aliphati- εche, cycloaliphatische, aliphatisch-aromatische und aromatische Diamine bzw. Aminoalkohole, vorzugsweise mit 2 bis 44 Kohlen- stoffatomen. Hierzu gehören u.a. auch A ine aus dimeren Fettsäu¬ ren. Zwischen den beiden Aminofunktionen der Diamine können sich in der Kohlenwasserstoffkette oder am cycloaliphatischen oder aromatischen Rest zusätzliche strukturelle Elemente bzw. weitere funktioneile Gruppen, z.B. Ethergruppen, Diamidgruppierungen, Aminogruppen, Ketogruppen oder Sulfongruppen befinden. Bevorzugt eingesetzte Diamine sind 1,2-Diaminoethan, 1,3-Diaminopropan, 1,6-Diaminohexan, 1,8-Diaminooctan, Piperazin, Diethylentriamin, 4,7,10-Trioxatridecan-l,13-diamin, 3,3'-Diaminodiphenylsulfon, 3,3'-Dimethyl-4r4 -diaminodicyclohexylmethan und handelsübliche Etherdiamine der FormelTriglycerides containing epoxy groups can be linked together, for example, with diols, diamines and amino alcohols. As diamines or amino alcohols are primary and secondary aliphatic, cycloaliphatic, aliphatic-aromatic and aromatic diamines or amino alcohols, preferably having 2 to 44 carbon atoms. These also include amines from dimeric fatty acids. Between the two amino functions of the diamines, there may be additional structural elements or further functional groups, for example ether groups, diamide groups, amino groups, keto groups or sulfone groups, in the hydrocarbon chain or on the cycloaliphatic or aromatic radical. Diamines used with preference are 1,2-diaminoethane, 1,3-diaminopropane, 1,6-diaminohexane, 1,8-diaminooctane, piperazine, diethylenetriamine, 4,7,10-trioxatridecane-l, 13-diamine, 3,3 ' -Diaminodiphenylsulfone, 3,3'-dimethyl-4 r 4 -diaminodicyclohexylmethane and commercially available ether diamines of the formula
CH3 / H_N-CHCH. [ OCH.CH ] nNH2 CH 3 / H_N-CHCH. [OCH.CH] n NH 2
CH3 CH 3
wobei n eine ganze Zahl von 1 bis ungefähr 2000 sein kann. Besonders bevorzugt werden 1,2-Diaminoethan und 1,6-Diaminohexan eingesetzt. Bevorzugte Aminoalkohole sind 2-Aminoethanol und 3- Aminopropanol.where n can be an integer from 1 to about 2000. 1,2-Diaminoethane and 1,6-diaminohexane are particularly preferably used. Preferred amino alcohols are 2-aminoethanol and 3-aminopropanol.
Für die Umsetzung geeignete Diole sind primäre und sekundäre aliphatische, cycloaliphatische, aliphatisch-aromatische und aromatische Diole, vorzugsweise mit 2 bis 44 Kohlenstoffatomen. Bevorzugt eingesetzt werden Glycol, 1,4-Butandiol, 2-Butin-l,4- diol, 2-Buten-l,4-diol, 1,5-Pentandiol, 1,6-Hexandiol, 1,10- Decandiol, Neopentylglycol, N,N-Diethylamino-propandiol-2,3 oder Hydroxypivalinsäureneopentylglycolester. Besonders bevorzugt sind 1,4-Butandiol und 1,10-Decandiol. Die Umsetzung der Reaktionsko ponenten erfolgt zweckmäßig in einem Temperaturbereich zwischen 20 und 200°C.Suitable diols for the reaction are primary and secondary aliphatic, cycloaliphatic, aliphatic-aromatic and aromatic diols, preferably having 2 to 44 carbon atoms. Glycol, 1,4-butanediol, 2-butyne-1,4-diol, 2-butene-1,4-diol, 1,5-pentanediol, 1,6-hexanediol, 1,10-decanediol, neopentyl glycol are preferably used , N, N-diethylamino-propanediol-2,3 or hydroxypivalic acid neopentyl glycol ester. 1,4-Butanediol and 1,10-decanediol are particularly preferred. The reaction components are expediently carried out in a temperature range between 20 and 200.degree.
Dem Reaktionsgemisch können die in der Kunststoffherεtellung üblichen Katalysatoren und Stabilisatoren zugesetzt werden. Die Umsetzung kann in Lösung oder in der Schmelze erfolgen. Zweckmä¬ ßig arbeitet man unter einer Inertgasatmoεphäre.The catalysts and stabilizers customary in plastics production can be added to the reaction mixture. The reaction can take place in solution or in the melt. It is expedient to work under an inert gas atmosphere.
Die nach dem erfindungsgemäßen Verfahren erhältlichen Kunststof¬ fe sind transparent und duroplaεtiεch. Ihre Eigenεchaften hängen im wesentlichen von der Art der Ausgangsöle und -fette, dem Oxidations- und Vernetzungεgrad, sowie der Art der bi- oder multifunktionellen Verbindungen und deren molarem Mischungs¬ verhältnis zu den oxidierten Triglyceriden ab. Ganz generell sind auch hier die allgemeinen Regeln der klassischen Polymer¬ chemie zu berücksichtigen. Bevorzugt wird die Menge an bi- oder multifunktioneller Verbindung so gewählt, daß der Anteil der reaktiven Gruppen dieser Verbindungen bezogen auf die Hydroxy- oder Epoxygruppen im Triglycerid zwischen 0,5 und 1,5 liegt. Bei Verwendung von stark oxidierten Triglyceriden, wie sie bei¬ spielsweise aus Euphorbiaöl oder ölsäurereichem Sonnenblumenöl mit einem Ölsäuregehalt von 85 % erhältlich εind, laεsen sich die Kunstεtoffeigenschaften besonders leicht variieren, weil hier das zu Polymeren führende Mischungsverhältnis von oxidier¬ ten Triglyceriden zu bi- oder multifunktioneller Verbindung besonders breit ist. Der Oxidationsgrad und der Anteil an bi- oder multifunktioneller Verbindung wird umso höher gewählt werden, je stärker die Vernetzung erfolgen soll. Mit der Anzahl der Hydroxylgruppen erhöhen sich außerdem Hydrophilie und Ad- sorptivität, d.h. die Anlagerungsfähigkeit des Kunststoffs an andere Stoffe wie beispielεweise Glas, Lacke und Metalle. Durch das erfindungεgemäße Verfahren iεt es nunmehr gelungen, auch solche Fette und Öle für die Kunεtstoffverarbeitung zugäng¬ lich zu machen, die vorher wegen ihrer störenden Begleitstoffe nicht nutzbar waren. Die vorliegende Erfindung ermöglicht hier¬ bei nicht nur eine einfaöhe sondern auch eine kostengünεtige Bereitstellung von technisch nützlichen Produkten und Zwischen¬ produkten. The plastics obtainable by the process according to the invention are transparent and thermoset. Their properties essentially depend on the type of starting oils and fats, the degree of oxidation and crosslinking, as well as the type of bi- or multifunctional compounds and their molar mixing ratio to the oxidized triglycerides. In general, the general rules of classic polymer chemistry must also be taken into account here. The amount of bi- or multifunctional compound is preferably selected so that the proportion of the reactive groups of these compounds, based on the hydroxyl or epoxy groups in the triglyceride, is between 0.5 and 1.5. When using strongly oxidized triglycerides, such as those obtainable from euphorbia oil or oleic sunflower oil with an oleic acid content of 85%, the properties of the plastics can be varied particularly easily, because here the mixing ratio of oxidized triglycerides leading to polymers is to be bi- or multifunctional connection is particularly wide. The higher the degree of crosslinking, the higher the degree of oxidation and the proportion of bi- or multifunctional compound. The number of hydroxyl groups also increases the hydrophilicity and adsorptivity, ie the ability of the plastic to attach to other substances such as glass, lacquers and metals. The method according to the invention has now made it possible to also make fats and oils accessible for plastic processing which previously could not be used because of their disruptive accompanying substances. The present invention enables not only simple but also inexpensive provision of technically useful products and intermediate products.

Claims

Patentansprüche Claims
1. Verfahren zur Herstellung von Kunεtεtoffcomonomeren und Kunststoffen aus Fetten und Ölen mit ungesättigten Fett¬ säuren, dadurch gekennzeichnet, daß man rohe ungeεättigte Fette und Öle mit Perameiεensäure oder Peressigsäure, vor¬ zugsweise in Ameisensäure oder Essigsäure als Löεungsmittel zu Epoxy- oder Hydroxyverbindungen oxidiert und zur Her- εtellung von Kunststoffen anschließend vorzugsweise direkt in an sich bekannter Weise mit bi- oder multifunktionellen Verbindungen, die zur Reaktion mit Epoxy- oder Hydroxy¬ gruppen in der Lage sind, zu Polymeren umsetzt.1. A process for the preparation of Kunεtεtoffcomonomeren and plastics from fats and oils with unsaturated fatty acids, characterized in that raw unsaturated fats and oils with performic acid or peracetic acid, preferably in formic acid or acetic acid as a solvent to epoxy or hydroxy compounds and oxidized for the production of plastics, then preferably directly in a manner known per se with bi- or multifunctional compounds which are capable of reacting with epoxy or hydroxyl groups to form polymers.
2. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß als Ausgangsmaterial rohe Fette und Öle eingesetzt werden, in denen der Anteil an ungesättigten Fettsäureresten, bezogen auf die Gesamtzahl von Fettsäureresten, wenigstens 50 % beträgt.2. The method according to claim 1, characterized in that raw fats and oils are used as starting material in which the proportion of unsaturated fatty acid residues, based on the total number of fatty acid residues, is at least 50%.
3. Verfahren nach Anspruch 1 oder 2, dadurch gekennzeichnet, daß als Ausgangsmaterial die rohen Öle der Euphorbia lathy- ris oder von ölsäurereichen Sonnenblumen, insbesondere der Art "High oleic", eingesetzt werden.3. The method according to claim 1 or 2, characterized in that the raw oils of Euphorbia lathy-ris or oleic acid-rich sunflowers, in particular of the "high oleic" type, are used as the starting material.
4. Verfahren nach einem der Ansprüche 1 bis 3, dadurch gekenn¬ zeichnet, daß die Perameiεenεäure oder die Peressigεäure durch Reaktion der als Lösungεmittel verwendeten Ameisen¬ säure bzw. Eεεigsäure mit H202 in situ im Reaktionsgemiεch erzeugt wird. 4. The method according to any one of claims 1 to 3, characterized gekenn¬ characterized in that the performic acid or the peracetic acid by reaction of the formic acid used as solvent or acetic acid with H 2 0 2 is generated in situ in the reaction mixture.
5. Verfahren nach einem der Ansprüche 1 bis 4, dadurch gekenn¬ zeichnet, daß die Oxidation bei Temperaturen von -5 bis +80°C stattfindet.5. The method according to any one of claims 1 to 4, characterized gekenn¬ characterized in that the oxidation takes place at temperatures from -5 to + 80 ° C.
6. Verfahren nach einem der Ansprüche 1 bis 5, dadurch gekenn¬ zeichnet, daß die bifunktionellen Verbindungen, mit denen die oxidierten Fette und Öle umgesetzt werden Di- oder Polyisocyanate sind.6. The method according to any one of claims 1 to 5, characterized gekenn¬ characterized in that the bifunctional compounds with which the oxidized fats and oils are reacted are di- or polyisocyanates.
7. Verfahren nach einem der Ansprüche 1 bis 5, dadurch gekenn¬ zeichnet, daß die'bifunktionellen Verbindungen, mit denen die oxidierten Fette und Öle umgesetzt werden, Dicarbonsäu- ren oder ihre Derivate, insbesondere Säuredichloride sind.7. The method according to any one of claims 1 to 5, characterized gekenn¬ characterized in that the bifunctional compounds with which the oxidized fats and oils are reacted are dicarboxylic acids or their derivatives, especially acid dichlorides.
8. Verfahren nach einem der Anεprüche 1 bis 5, dadurch gekenn¬ zeichnet, daß die bifunktionellen Verbindungen, mit denen die Epoxyverbindungen umgesetzt werden, Diole, Diamine oder Aminoalkohole sind. 8. The method according to any one of claims 1 to 5, characterized gekenn¬ characterized in that the bifunctional compounds with which the epoxy compounds are reacted are diols, diamines or amino alcohols.
EP19900912681 1989-08-09 1990-08-01 Process for preparing plastics from raw fats and oils Withdrawn EP0437592A1 (en)

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