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WO2003031494A1 - Polyester - Google Patents

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Publication number
WO2003031494A1
WO2003031494A1 PCT/EP2002/010665 EP0210665W WO03031494A1 WO 2003031494 A1 WO2003031494 A1 WO 2003031494A1 EP 0210665 W EP0210665 W EP 0210665W WO 03031494 A1 WO03031494 A1 WO 03031494A1
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WO
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Prior art keywords
oil
process according
epoxidized
anhydride
carboxylic acid
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Ceased
Application number
PCT/EP2002/010665
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German (de)
French (fr)
Inventor
Horst Sulzbach
Michael Skwiercz
Ralf Bemmann
Thorsten Roloff
Rainer HÖFER
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BASF Personal Care and Nutrition GmbH
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Cognis Deutschland GmbH and Co KG
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Publication of WO2003031494A1 publication Critical patent/WO2003031494A1/en
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • 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
    • C08G59/20—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 epoxy compounds used
    • C08G59/32—Epoxy compounds containing three or more epoxy groups
    • 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
    • C08G59/42—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof

Definitions

  • the present invention relates to polyesters obtained by reacting epoxidized triglycerides with suitable anhydrides, a process for the preparation of the polyesters and the use of certain carboxylic anhydrides for the production of polyesters
  • Carboxylic anhydrides have long been known as so-called hot hardeners of petrochemically based epoxides, for example bisphenol A diglycidyl ethers. It is also known that certain anhydrides can be used to cure fat based epoxies. The polyesters formed in such curing reactions are suitable, for example, as a matrix material for the production of composite materials.
  • DD 48 687 describes the reaction of epoxidized soybean oil with valley anhydrides with the simultaneous addition of adipic acid.
  • WO 97/02307 discloses composite materials of a matrix based on polyester, the polyesters being produced from epoxidized fats and oils, carboxylic acid anhydrides and polycarboxylic acids. From the publication by Rösch et. al., Polymer Bulletin 31, 1993, page 679, describes the physical properties of polyester which are obtainable by curing epoxidized soybean oils with carboxylic acid anhydrides.
  • a first subject of the present application therefore relates to a process for the preparation of polyesters, in which epoxidized triglycerides are reacted in the presence of alkyl-substituted carboxylic acid anhydrides which are liquid at 21 ° C. and further catalysts are reacted at elevated temperature.
  • the epoxidized triglycerides used in the process according to the invention are known to the person skilled in the art. It is preferably epoxidized soybean oil, epoxidized cottonseed oil, epoxidized olive oil, epoxidized olive oil-epoxidized linseed oil, epoxidized linola oil], epoxidized sesame oil, epoxidized sunflower oil, epoxidized rapeseed oil and epoxidized castor oil or mixtures of these epoxies. It is preferred if the epoxidized triglycerides have an epoxide content of ind.
  • carboxylic acid anhydrides When selecting suitable carboxylic acid anhydrides, it is essential that the compounds are liquid at 21 ° C, i.e. room temperature.
  • the carboxylic acid anhydrides must be structured so that the anhydride is attached to an aiphatic ring. Furthermore, this cyclic, aromatic compound must be alkyl, and preferably methyl or ethyl substituted. It has also been shown that preference is given to using carboxylic anhydrides in which the two carboxyl groups are conjugated.
  • alkyl- preferably methyl-substituted derivatives of cyclopentanedicarboxylic anhydride, cyclohexanedicarboxylic anhydride, cycloheptane which are liquid at room temperature.
  • Unsaturated derivatives can also be used.
  • isomeric methylcyclohexane carboxylic anhydride is very particularly preferred.
  • Methylcyclohexenecarboxylic anhydride is also preferred.
  • the process according to the invention is carried out at temperatures of 100 to 200 ° C. and preferably 150 to 200 ° C.
  • catalysts are also essential to the invention, it being possible here in particular to use N-methylimidazoles.
  • suitable catalysts are, for example Alumim 'umacetylacetonat, benzyl or 2-ethylimidazole, but other compounds known as Epoxidharzbechan, preferably 2,4,6-tris (dimethylaminoethyl) phenol (Versamine EH 30, Cognis Corp.) and bis-N , N- (dimethylaminopropy ⁇ ) urea (Versamine EH 50, Cognis Corp.).
  • the reaction time is generally between 1 and 80 minutes, preferably between 20 and 60 minutes.
  • the polyesters obtained by the process according to the invention are notable in particular for their high Shore D hardness, which is at least 70, preferably 75 and in particular 80>.
  • the molar ratio between carboxylic acid anhydrides and epoxidized triglycerides is preferably in the range from 1: 1 to 1: 2.
  • the catalysts are also used in amounts which are known to those skilled in the art for such reactions, preferably in amounts of 0.5 to 2% by weight. % based on the mixture of anhydrides and epoxides.
  • the polyesters according to the invention show low fogging and are therefore preferably suitable for use in materials, e.g. fiber-reinforced composite materials, for the interior of automobiles.
  • the present invention further relates to the use of alkyl and preferably methyl-substituted carboxylic anhydrides which are liquid at 21 ° C. for curing fatty acid triglyceride epoxides.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Polyesters Or Polycarbonates (AREA)

Abstract

The invention relates to a method for producing polyesters during which epoxidized triglycerides are reacted at high temperatures in the presence of cyclic alkyl-substituted carboxylic acid anhydrides, which are liquid at 21 DEG C, and of catalysts.

Description

"Polyester" "Polyester"

Die vorliegende Erfindung betrifft Polyester, die durch Umsetzung epoxydierter Triglyceride mit geeigneten Ahnhydriden erhalten werden, weiterhin ein Verfahren zur Herstellung der Polyester und die Verwendung bestimmter Carbonsäureanhydride zur Herstellung von PolyestemThe present invention relates to polyesters obtained by reacting epoxidized triglycerides with suitable anhydrides, a process for the preparation of the polyesters and the use of certain carboxylic anhydrides for the production of polyesters

Carbonsäureanhydride sind seit langem als sogenannte Heißhärter von petrochemisch basierten Epoxiden, beispielsweise Bisphenol- A-Diglycidylethern bekannt. Es ist auch bekannt, dass bestimmte Anhydride zum Aushärten fettbasierter Epoxide verwendet werden können. Die bei derartigen Härtungsreaktionen entstehenden Polyester eignen sich beispielsweise als Matrixmaterial zur Herstellung von Verbundwerkstoffen.Carboxylic anhydrides have long been known as so-called hot hardeners of petrochemically based epoxides, for example bisphenol A diglycidyl ethers. It is also known that certain anhydrides can be used to cure fat based epoxies. The polyesters formed in such curing reactions are suitable, for example, as a matrix material for the production of composite materials.

Aus dem Stand der Technik, beispielsweise der DD 48 687 ist die Umsetzung epoxidierten Sojaöls mit Talsäureanhydriden unter gleichzeitigem Zusatz von Adipinsäure beschrieben. In der WO 97/02307 werden Verbundwerkstoffe einer Matrix auf Basis von Polyestem offenbart, wobei die Polyester hergestellt werden aus epoxidierten Fetten und Ölen, Carbonsaureanhydriden und Polycarbonsäuren. Aus der Veröffentlichung von Rösch et. al., Polymer Bulletin 31, 1993, Seite 679, werden die physikalischen Eigenschaften beschrieben von Polyestem, die erhältlich sind durch Aushärtung von epoxidiertem Sojaölen mit Carbonsaureanhydriden.The prior art, for example DD 48 687, describes the reaction of epoxidized soybean oil with valley anhydrides with the simultaneous addition of adipic acid. WO 97/02307 discloses composite materials of a matrix based on polyester, the polyesters being produced from epoxidized fats and oils, carboxylic acid anhydrides and polycarboxylic acids. From the publication by Rösch et. al., Polymer Bulletin 31, 1993, page 679, describes the physical properties of polyester which are obtainable by curing epoxidized soybean oils with carboxylic acid anhydrides.

Bei dem aus dem Stand der Technik bekannten Verfahren stellt sich aber häufig das Problem, dass z. B. die Carbonsäureanliydride relativ unreaktiv sind. Weiterhin hydrolysieren die zur Aushärtung der Fettepoxide verwendeten Anhydride bei der Lagerung an der Luft aufgrund ihrer kristallinen Struktur sehr schnell und können daher nur mit entsprechendem Aufwand umgesetzt werden.In the method known from the prior art, however, the problem frequently arises that, for. B. the Carbonsäureanliydride are relatively unreactive. Furthermore, the anhydrides used to harden the fat epoxides hydrolyze very quickly when stored in the air due to their crystalline structure and can therefore only be reacted with corresponding effort.

Es war die Aufgabe der vorliegenden Erfindung, Carbonsäureanhydride zur Umsetzung mit Fettepoxiden zu finden, welche gegenüber Luftfeuchtigkeit vergleichsweise stabil sind und nahezu vollständig zu Polyestem abreagieren, ohne dass dazu beispielsweise noch Polyoarbonsäuren in größeren Mengen vorliegen müssen.It was the object of the present invention to find carboxylic anhydrides for reaction with fat epoxides which are comparatively stable with respect to atmospheric moisture and react almost completely to polyester, without the need for example to have large amounts of polyoarboxylic acids present.

Es wurde befunden, dass bestimmte substituierte Carbonsätireanhydride die oben gewünschten Eigenschaften aufweisen.It has been found that certain substituted carboxylic acid anhydrides have the properties desired above.

Ein erster Gegenstand der vorliegenden Anmeldung betrifft daher ein Verfahren zur Herstellung von Polyestem, wobei man epoxidierte Triglyceride in Gegenwart von bei 21 °C flüssigen alkylsubstituierten Carbonsaureanhydriden und weiterhin Katalysatoren bei erhöhter Temperatur zur Reaktion bringt.A first subject of the present application therefore relates to a process for the preparation of polyesters, in which epoxidized triglycerides are reacted in the presence of alkyl-substituted carboxylic acid anhydrides which are liquid at 21 ° C. and further catalysts are reacted at elevated temperature.

Die im erfmdungsgemäßen Verfahren eingesetzten epoxidierten Triglyceride sind dem Fachmann bekannt. Es handelt es sich dabei vorzugsweise um epoxidiertes Sojaöl, epoxidiertes Baumwollsamenöl, epoxidiertes Olivenöl, epoxidiertes Olivenkernöl- epoxidiertes Leinöl, epoxidiertes Linolaö], epoxidiertes Sesamöl, epoxidiertes Sonnenblumenöl, epoxidiertes Rapsöl und epoxidiertes Rizinusöl bzw. Mischungen dieser Epoxide. Bevorzugt ist es, wenn die epoxidierten Triglyceride einen Epoxidgehalt von ind. 5 Gew.-%f aber vorzugsweise von 6 bis 8,5 Gew.~% aufweisen. Steigt der Anteil des Epoxids deutlich über 8 Gew.-% an, so kommt es allerdings zu einer sehr schnellen Aushärtung der Epoxide an der Luft, welche nicht gewünscht ist.The epoxidized triglycerides used in the process according to the invention are known to the person skilled in the art. It is preferably epoxidized soybean oil, epoxidized cottonseed oil, epoxidized olive oil, epoxidized olive oil-epoxidized linseed oil, epoxidized linola oil], epoxidized sesame oil, epoxidized sunflower oil, epoxidized rapeseed oil and epoxidized castor oil or mixtures of these epoxies. It is preferred if the epoxidized triglycerides have an epoxide content of ind. 5 wt .-% f but preferably from 6 to 8.5 wt .-% have. If the proportion of the epoxide rises significantly above 8% by weight, however, the epoxides cure very quickly in the air, which is not desired.

Bei der Auswahl der geeigneten Carbonsäureanhydride ist es wesentlich, dass es sich dabei um bei 21 °C, also Raumtemperatur, flüssigen Verbindungen handelt. Die Carbonsäureanhydride müssen strukturell so aufgebaut sein, dass das Anhydrid an einem aiiphatischen Ring gebunden ist. Weiterhin muss diese cyciische aüphatische Verbindung Alkyl, und vorzugsweise Methyl- oder Ethylsubstitαiert sein. Es hat sich, auch gezeigt, dass vorzugsweise solche Carbonsäureanhydridε eingesetzt werden, bei denen die zwei Carboxylgruppen konjugiert sind.When selecting suitable carboxylic acid anhydrides, it is essential that the compounds are liquid at 21 ° C, i.e. room temperature. The carboxylic acid anhydrides must be structured so that the anhydride is attached to an aiphatic ring. Furthermore, this cyclic, aromatic compound must be alkyl, and preferably methyl or ethyl substituted. It has also been shown that preference is given to using carboxylic anhydrides in which the two carboxyl groups are conjugated.

Besonders bevorzugt im Rahmen des vorliegenden erfmdungsgemäßen Verfahrens sind die bei Raumtemperatur flüssigen, alkyl- vorzugsweise methylsubstituierten Derivate von Cyclopentandicarbonsäureanhydrid, Cyclohexandicarbonsäureanhydrid, Cycloheptan- dicarbonsäureanhydrid bzw. deren Mischungen. Auch ungesättigte Derivate können eingesetzt werden.Particularly preferred in the context of the present inventive method are the alkyl- preferably methyl-substituted derivatives of cyclopentanedicarboxylic anhydride, cyclohexanedicarboxylic anhydride, cycloheptane which are liquid at room temperature. dicarboxylic anhydride or mixtures thereof. Unsaturated derivatives can also be used.

Ganz besonders bevorzugt ist der Einsatz von isomerem Methylcyclohexan- carbonsäureanhydrid. Auch das Methylcyclohexencarbonsäureanhydrid ist bevorzugt.The use of isomeric methylcyclohexane carboxylic anhydride is very particularly preferred. Methylcyclohexenecarboxylic anhydride is also preferred.

Das erfindungsgemäße Verfahren wird, bei Temperaturen von 100 bis 200 °C und vorzugsweise 150 bis 200 °C durchgeführt. Weiterhin erfindungswesentlich ist der Zusatz geringer Mengen an Katalysatoren, wobei hier insbesondere N-Methylimidazole eingesetzt werden können. Andere geeignete Katalysatoren sind beispielsweise Alumim'umacetylacetonat, Benzyldimethylamin oder 2-Ethylimidazol, aber auch andere als Epoxidharzbeschleuniger bekannte Verbindungen, vorzugsweise 2,4,6-Tris- (dimethylaminoethyl)-phenol (Versamine EH 30, Cognis Corp.) und Bis-N,N- (dimethylaminopropyι)-harnstoff (Versamine EH 50, Cognis Corp.).The process according to the invention is carried out at temperatures of 100 to 200 ° C. and preferably 150 to 200 ° C. The addition of small amounts of catalysts is also essential to the invention, it being possible here in particular to use N-methylimidazoles. Other suitable catalysts are, for example Alumim 'umacetylacetonat, benzyl or 2-ethylimidazole, but other compounds known as Epoxidharzbeschleuniger, preferably 2,4,6-tris (dimethylaminoethyl) phenol (Versamine EH 30, Cognis Corp.) and bis-N , N- (dimethylaminopropyι) urea (Versamine EH 50, Cognis Corp.).

Die Reaktionszeit beträgt in der Regel zwischen 1 und 80 Minuten, vorzugsweise zwischen 20 und 60 Minuten. Die durch das erfindungsgemäße Verfahren erhaltenen Polyester zeichnen sich insbesondere durch ihre große Shore-D-Härte aus, die beim mind. 70, vorzugsweise 75 und insbesondere bei 80 > liegt. Das molare Verhältnis zwischen Carbonsaureanhydriden und epoxilierten Triglyceriden liegt vorzugsweise im Bereich 1 : 1 bis 1 : 2. Die Katalysatoren werden ebenfalls in Mengen, die dem Fachmann für derartige Reaktionen bekannt sind, eingesetzt, vorzugsweise in Mengen von 0,5 bis 2 Gew.-% bezogen auf die Mischung aus Anhydriden und Epoxiden. Weitrhin zeigen die erfindungsgemäßen Polyester ein geringes Fogging und eignen sich daher vorzugsweise zur Verwendung in Werkstoffen, z.B. faserverstärkte Verbundwerkstoffe, für den Innenraum von Automobilen.The reaction time is generally between 1 and 80 minutes, preferably between 20 and 60 minutes. The polyesters obtained by the process according to the invention are notable in particular for their high Shore D hardness, which is at least 70, preferably 75 and in particular 80>. The molar ratio between carboxylic acid anhydrides and epoxidized triglycerides is preferably in the range from 1: 1 to 1: 2. The catalysts are also used in amounts which are known to those skilled in the art for such reactions, preferably in amounts of 0.5 to 2% by weight. % based on the mixture of anhydrides and epoxides. Furthermore, the polyesters according to the invention show low fogging and are therefore preferably suitable for use in materials, e.g. fiber-reinforced composite materials, for the interior of automobiles.

Ein weiterer Gegenstand der vorliegenden Erfindung betrifft die Verwendung von bei 21 °C flüssigen alkyl- und vorzugsweise methylsubstituierten Carbonsaureanhydriden zur Härtung von Fettsäuretriglyceridepoxiden. BeispieleThe present invention further relates to the use of alkyl and preferably methyl-substituted carboxylic anhydrides which are liquid at 21 ° C. for curing fatty acid triglyceride epoxides. Examples

A) Eine Mischung aus 12 g Leinölepoxid (Epoxidgehalt ca. 8,2 g) wurde mit 8 g isomerem Methylcyclohexancarbonsäureanhydrid in Gegenwart von 0,125 g N- Methylimidazol in einem Aluminiumbecher bei 180 °C 30 Minuten erhitzt. Der erhaltene Polyester wies eine Shore-D Härte von 80 auf.A) A mixture of 12 g linseed oil epoxide (epoxy content approx. 8.2 g) was heated with 8 g isomeric methylcyclohexanecarboxylic acid anhydride in the presence of 0.125 g N-methylimidazole in an aluminum beaker at 180 ° C. for 30 minutes. The polyester obtained had a Shore D hardness of 80.

B) Eine Mischung aus 12 g Leinölepoxid (Epoxidgehalt ca. 8,2 g) wurde mit 8 g isomerem Methylcyclohexancarbonsäureanhydrid in Gegenwart von 1,0 g Versamine-EH 30 in einem Aluminiumbecher bei 180 °C 30 Minuten erhitzt. Der erhaltene Polyester wies eine Shore-D Härte von 85 auf.B) A mixture of 12 g linseed oil epoxide (epoxy content approx. 8.2 g) was heated with 8 g isomeric methylcyclohexanecarboxylic acid anhydride in the presence of 1.0 g Versamine-EH 30 in an aluminum beaker at 180 ° C for 30 minutes. The polyester obtained had a Shore D hardness of 85.

C) Eine Mischung aus 12 g Leinölepoxid (Epoxidgehalt ca. 8,2 g) wurde mit 8 g isomerem Methylcyclohexancarbonsäureanhydrid in Gegenwart von 1,0 g Versamine-EH 50 in einem Aluminiumbecher bei 180 °C 30 Minuten erhitzt. Der erhaltene Polyester wies eine Shore-D Härte von 80 auf. C) A mixture of 12 g linseed oil epoxide (epoxy content approx. 8.2 g) was heated with 8 g isomeric methylcyclohexanecarboxylic acid anhydride in the presence of 1.0 g Versamine-EH 50 in an aluminum beaker at 180 ° C for 30 minutes. The polyester obtained had a Shore D hardness of 80.

Claims

Patentansprüche claims 1. Verfahren zur Herstellung von Polyestem, dadurch gekennzeichnet, daß man epoxidierte Triglyceride in Gegenwart von bei 21 °C flüssigen, cyclischen alkylsubstituierten Carbonsaureanhydriden und Katalysatoren bei erhöhten1. A process for the preparation of polyester, characterized in that epoxidized triglycerides in the presence of liquid at 21 ° C, cyclic alkyl-substituted carboxylic acid anhydrides and catalysts at elevated Temperaturen zur Reaktion bringt.Brings temperatures to reaction. 2. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß die epoxidierten Triglyceride einen Epoxidgehalt von mindestens 5 Gew.-%, vorzugsweise 6 bis 8,5 Gew.-% aufweisen.2. The method according to claim 1, characterized in that the epoxidized triglycerides have an epoxy content of at least 5 wt .-%, preferably 6 to 8.5 wt .-%. 3. Verfahren nach den Ansprüchen 1 bis 2, dadurch gekennzeichnet, daß die epoxidierten Triglyceride ausgewählt sind aus der Gruppe, epoxidiertes Sojaöl, Baumwollsamenöl, Olivenöl, Olivenkernöl, Leinöl, Linolaöl, Sesamöl, Sonnenblumenöl, Rapsöl, Ricinusöl.3. Process according to claims 1 to 2, characterized in that the epoxidized triglycerides are selected from the group consisting of epoxidized soybean oil, cottonseed oil, olive oil, olive kernel oil, linseed oil, linola oil, sesame oil, sunflower oil, rapeseed oil and castor oil. 4. Verfahren nach den Ansprüchen 1 bis 3, dadurch gekennzeichnet, daß die Carbonsäureanhydride ausgewählt sind aus der Gruppe der alkylsubstituierten Derivate von Cyclopentandicarbonsäureanhydrid, Cyclohexandicarbonsäureanhydrid und Cycloheptandicarbonsäureanhydrid oder deren Mischungen.4. Process according to claims 1 to 3, characterized in that the carboxylic anhydrides are selected from the group of the alkyl-substituted derivatives of cyclopentanedicarboxylic anhydride, cyclohexanedicarboxylic anhydride and cycloheptanedicarboxylic anhydride or mixtures thereof. 5. Verfahren nach den Ansprüchen 1 bis 4, dadurch gekennzeichnet, daß methyl- oder ethylsubstituierte cyciische Carbonsäureanhydride ausgewählt werden.5. Process according to claims 1 to 4, characterized in that methyl- or ethyl-substituted cyclic carboxylic anhydrides are selected. 6. Verfahren nach den Ansprüchen 1 bis 5, dadurch gekennzeichnet, daß isomeres Methylcyclohexancarbonsäureanhydrid eingesetzt wird.6. Process according to claims 1 to 5, characterized in that isomeric methylcyclohexane carboxylic acid anhydride is used. 7. Verfahren nach den Ansprüchen 1 bis 6, dadurch gekennzeichnet, daß es bei Temperaturen von 100 bis 200 °C, vorzugsweise 150 bis 200 °C durchgeführt wird.7. Process according to claims 1 to 6, characterized in that it is carried out at temperatures of 100 to 200 ° C, preferably 150 to 200 ° C. 8. Verfahren nach den Ansprüchen 1 bis 7, dadurch gekennzeichnet, daß das molare Verhältnis von Carbonsäureanhydrid zu epoxidiertem Triglycerid im Bereich von 1 : 1 bis 1 : 2 liegt. 8. Process according to claims 1 to 7, characterized in that the molar ratio of carboxylic acid anhydride to epoxidized triglyceride is in the range from 1: 1 to 1: 2. 9. Verfahren nach den Ansprüchen 1 bis 8, dadurch gekennzeichnet, daß als Katalysator N-Methylimidazol eingesetzt wird.9. The method according to claims 1 to 8, characterized in that N-methylimidazole is used as catalyst. 10. Polyester, erhältlich durch ein Verfahren nach den Ansprüchen 1 bis 9, dadurch gekennzeichnet, daß der Polyester eine Shore-D-Härte von mindestens 70 vorzugsweise 75 und insbesondere 80 aufweist.10. Polyester, obtainable by a process according to claims 1 to 9, characterized in that the polyester has a Shore D hardness of at least 70, preferably 75 and in particular 80. 11. Verwendung von bei 21 °C flüssigen alkylsubsituierten Carbonsaureanhydriden zur Härtung von Fettsäuretriglyceridepoxiden. 11. Use of alkyl-substituted carboxylic acid anhydrides which are liquid at 21 ° C. for curing fatty acid triglyceride epoxides.
PCT/EP2002/010665 2001-10-02 2002-09-23 Polyester Ceased WO2003031494A1 (en)

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DE10148672.3 2001-10-02
DE2001148672 DE10148672A1 (en) 2001-10-02 2001-10-02 Production of polyester involves reacting epoxidised triglyceride at elevated temperature with liquid, alkyl-substituted, cyclic carboxylic acid anhydride in presence of catalyst

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