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WO2010089264A1 - Method for producing bicarbonates - Google Patents

Method for producing bicarbonates Download PDF

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Publication number
WO2010089264A1
WO2010089264A1 PCT/EP2010/051141 EP2010051141W WO2010089264A1 WO 2010089264 A1 WO2010089264 A1 WO 2010089264A1 EP 2010051141 W EP2010051141 W EP 2010051141W WO 2010089264 A1 WO2010089264 A1 WO 2010089264A1
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Prior art keywords
carbonate
alkylene
compound
groups
alkylene carbonate
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PCT/EP2010/051141
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German (de)
French (fr)
Inventor
Rainer Klopsch
Jan Philipp Weyrauch
Kai Gumlich
Joaquim Henrique Teles
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BASF SE
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BASF SE
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D317/00—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms
    • C07D317/08—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3
    • C07D317/10—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 not condensed with other rings
    • C07D317/32—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 not condensed with other rings with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D317/34—Oxygen atoms
    • C07D317/36—Alkylene carbonates; Substituted alkylene carbonates
    • 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
    • C08G59/14—Polycondensates modified by chemical after-treatment
    • C08G59/1433—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds
    • C08G59/1438—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds containing oxygen

Definitions

  • the invention relates to a process for preparing compounds having at least two alkylene carbonate groups (abbreviated to alkylene carbonate) by reacting a compound having at least two alkylene oxide groups (abbreviated to alkylene oxide) with carbon dioxide, in which the reaction is carried out at a pressure of 12 to 40 bar.
  • Bisalkylencarbonates such as the biscarbonate of bisphenol A bisglycidyl ether, are important as starting materials for the preparation of polyurethanes. In particular, they can be used after reaction with an excess of amine compounds as amine hardeners for epoxides, as described in EP-A 661 363.
  • WO 84/03701, DE-A 3 529 263, DE-A 3600602 and DE-A 26 11 087 may be mentioned as state of the art for the production.
  • DE-A 3 529 263 and DE-A 3600602 describe the preparation of biscarbonates. According to DE-A 3529 263, the reaction of the alkylene oxide, e.g. carried out with carbon dioxide at atmospheric pressure or slightly elevated pressure.
  • DE-A 36 00 602 discloses a pressure of 1 to 98 bar, preferably a pressure of 1 to 10, in particular 1 to 3, bar.
  • WO 84/03701 and DE-A 26 11 087 describe the preparation of monoalkylene carbonates, such as ethylene carbonate or propylene carbonate. In the examples of WO 84/03701 takes place at 21 bar, DE-A 26 11 087 discloses a preferred range of 1 to 30 atmospheres.
  • the object of the present invention was to provide such a method.
  • a compound having at least two alkylene oxide groups is reacted with carbon dioxide to form a compound having at least two alkylene carbonate groups.
  • the carbon dioxide is added to the alkylene oxide group to form the cyclic alkylene carbonate group.
  • compounds having 2 to 4 alkylene oxide groups are suitable.
  • Particularly preferred is a compound having two Glyidylethergrup- pen, which to the corresponding Bisalkylencarbonat of formula I.
  • the radical R in formula I stands for any organic group having 2 to 30 C atoms, preferably 6 to 30 C atoms and in particular 12 to 24 C atoms.
  • the radical R can also contain heteroatoms such as oxygen, nitrogen and sulfur.
  • the radical R is a hydrocarbon group which contains no heteroatoms.
  • R is a hydrocarbon group which contains at least one, preferably one or two, more preferably two aromatic ring systems.
  • the aromatic ring system may be mentioned in particular the phenyl ring.
  • the bisalkylene carbonate is the
  • Bisphenol A bisglycerol carbonyl ethers of the formula II (4,4 '- ((1-methylethylidenes) bis (4,1-phenyleneoxymethylene)) bis (1,3-dioxolan-2-ones):
  • the starting compound is the bisphenol A bisglycidyl ether.
  • the reaction is carried out according to the invention at a pressure of 12 to 40 bar, preferably at a pressure of 12 to 35 bar and more preferably from 15 to 30 bar, in particular 20 to 30 bar.
  • the reaction is preferably carried out at a temperature of 50 to 150 0 C, more preferably at 60 to 100 0 C and most preferably at 70 to 90 ° C.
  • the reaction preferably takes place in the presence of a solvent.
  • the solvent is chosen so that the product of the reaction, for example the bisalkylene carbonate in the solvent is not or only slightly soluble and therefore can be separated as a solid from the reaction solution.
  • the alkylene carbonate is preferably at 20 0 C a solubility in the solvent used of not more than 20 parts by weight alkylene carbonate, especially a maximum of 10 parts by weight, more preferably at most 5 parts by weight of alkylene carbonate in 100 parts by weight of solvent.
  • Suitable solvents are, in particular, polar, aprotic solvents, for example tetrahydrofuran or dialkyl carbonates. Particularly preferred solvents are dialkyl carbonates, most preferably dimethyl carbonate.
  • the reaction is carried out in the presence of a catalyst.
  • catalysts are e.g. Phosphorus compounds having a trivalent phosphorus atom, e.g. tertiary phosphines such as trialkyl or triarylphosphine, or salts of quaternary ammonium compounds into consideration.
  • Phosphorus compounds having a trivalent phosphorus atom e.g. tertiary phosphines such as trialkyl or triarylphosphine, or salts of quaternary ammonium compounds into consideration.
  • Preferred salts of the quaternary ammonium compounds are those of the formula
  • R a , Rb, Rc and Rd independently represent a hydrocarbon group having 1 to 12 C-atoms, for example an alkyl or aryl group, and Y "is an anion, in particular a halide, particularly preferably a chloride.
  • Preferred salts of the quaternary ammonium compounds are the halides, especially chlorides and bromides.
  • Examples include benzyltrimethylammonium chloride or tetraethylammonium bromide.
  • the above salt of the quaternary ammonium compound may be used in combination with a metal salt.
  • a metal salt for example, metal halides such as alkali metal chlorides, alkali bromides, Alkaliiodi- de, zinc halides considered. Examples include potassium iodide and ZnBr2.
  • the amount of the catalysts used is preferably at least 0.1 part by weight, more preferably at least 0.3 part by weight and most preferably at least 0.5 part by weight per 100 parts by weight of alkylene oxide.
  • the amount of the catalysts used is preferably not more than 20 parts by weight, more preferably not more than 15 parts by weight per 100 parts by weight of alkylene oxide. In general, a content of between 0.5 and 10 parts by weight per 100 parts by weight of alkylene oxide is sufficient.
  • the implementation of the reaction can be carried out in a conventional manner in an autoclave.
  • the starting compounds i. the alkylene oxide, solvent and catalyst can be placed in the autoclave and then the desired pressure is set by introducing the gaseous carbon dioxide.
  • the resulting alkylene carbonate precipitates out of the reaction solution as a solid and can be easily separated after completion of the reaction.
  • the product obtained may optionally contain compounds in which not all alkylene oxide groups have been converted to alkylene carbonate groups.
  • the reaction is very simple and almost complete, so that more than 70 mol%, in particular more than 85 mol%, very particularly preferably more than 90 mol% of all alkylene oxide groups are converted into alkylene carbonate groups.
  • the epoxy number of the product obtained is preferably greater than 2000 and more preferably greater than 3000.
  • the epoxy number is the quotient of the mass of the product in grams and the number of moles of epoxy groups present. The lower the number of remaining epoxy groups, the greater the epoxy number.
  • the resulting alkylene carbonate, in particular bisalkylene carbonate is suitable as part of a two-component (2-K) system.
  • the one component (1st component) is the alkylene carbonate, in particular bisalkylene carbonate, alone or optionally in admixture with other compounds, the other (2.) component is preferably an amino compound or mixture of amino compounds.
  • the 2-component system can be used, for example, as a paint or adhesive system or for the production of composites.
  • amino compounds having at least two amino groups which may be secondary or primary amino groups, are suitable as the second component.
  • Preferred compounds having two secondary amino groups are in particular cyclic compounds such as piperazine.
  • Particularly preferred are amino compounds having at least two primary amino groups.
  • the two components are usually combined just before use. For amino compounds having more than two primary amino groups and a bisalkylene carbonate, crosslinked polymer systems are obtained.
  • Such a 2-component system represents an alternative to epoxy or PU systems.
  • the alkylene carbonate in particular bisalkylene carbonate
  • an amino compound having at least two primary or secondary amino groups Preferred compounds having two secondary amino groups are in turn cyclic compounds such as piperazine. Particularly preferred are amino compounds having at least two primary amino groups.
  • the amino groups are preferably present in excess in relation to the carbonate groups.
  • the molar ratio of the primary amino groups to the carbonate groups is 2: 1; e.g. Two moles of diamine are used per mole of bisalkylene carbonate.
  • the resulting reaction product then has the corresponding number of free, reactive amino groups and is suitable as an amine hardener for epoxy resins.
  • BGE carbonate is obtained as a colorless solid (melting point 148 to 150 ° C.), if appropriate mixed with unreacted educt.
  • a measure of the conversion of glycidyl groups into carbonate groups is the epoxy number (mass of products / mole of epoxy groups); the higher the epoxy number, the lower the content of epoxy groups. The epoxy number was determined according to DIN standard ASTM D 1652.
  • the examples marked V are comparative examples.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Emergency Medicine (AREA)
  • General Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

The invention relates to a method for producing compounds having at least two alkylene carbonate groups (referred to as alkylene carbonate for short) by reacting a compound having at least two alkylene oxide groups (referred to as alkylene oxide for short) with carbon dioxide, characterized in that the reaction occurs at a pressure of 12 to 40 bar.

Description

Verfahren zur Herstellung von Biscarbonaten Process for the preparation of biscarbonates

Beschreibungdescription

Die Erfindung betrifft ein Verfahren zur Herstellung von Verbindungen mit mindestens zwei Alkylencarbonatgruppen (kurz Alkylencarbonat genannt) durch Umsetzung einer Verbindung mit mindestens zwei Alkylenoxidgruppen (kurz Alkylenoxid genannt) mit Kohlendioxid, bei dem die Umsetzung bei einem Druck von 12 bis 40 bar erfolgt.The invention relates to a process for preparing compounds having at least two alkylene carbonate groups (abbreviated to alkylene carbonate) by reacting a compound having at least two alkylene oxide groups (abbreviated to alkylene oxide) with carbon dioxide, in which the reaction is carried out at a pressure of 12 to 40 bar.

Bisalkylencarbonate wie das Biscarbonat des Bisphenol-A-bisglycidylether sind als Ausgangstoffe für die Herstellung von Polyurethanen von Bedeutung. Insbesondere können sie nach Umsetzung mit einem Überschuss an Aminverbindungen als Amin- härter für Epoxide eingesetzt werden, wie in EP-A 661 363 beschrieben ist. Als Stand der Technik zur Herstellung seien WO 84/03701 , DE-A 3 529 263, DE-A 3600602 und DE-A 26 11 087 genannt.Bisalkylencarbonates, such as the biscarbonate of bisphenol A bisglycidyl ether, are important as starting materials for the preparation of polyurethanes. In particular, they can be used after reaction with an excess of amine compounds as amine hardeners for epoxides, as described in EP-A 661 363. WO 84/03701, DE-A 3 529 263, DE-A 3600602 and DE-A 26 11 087 may be mentioned as state of the art for the production.

DE-A 3 529 263 und DE-A 3600602 beschreiben die Herstellung von Biscarbonaten. Gemäß DE-A 3529 263 wird die Umsetzung des Alkylenoxids, z.B. mit Kohlendioxid bei Normaldruck oder geringfügig erhöhtem Druck durchgeführt. DE-A 36 00 602 of- fenbart einen Druck von 1 bis 98 bar, bevorzugt ist ein Druck von 1 bis 10, insbesondere 1 bis 3 bar.DE-A 3 529 263 and DE-A 3600602 describe the preparation of biscarbonates. According to DE-A 3529 263, the reaction of the alkylene oxide, e.g. carried out with carbon dioxide at atmospheric pressure or slightly elevated pressure. DE-A 36 00 602 discloses a pressure of 1 to 98 bar, preferably a pressure of 1 to 10, in particular 1 to 3, bar.

WO 84/03701 und DE-A 26 11 087 beschreiben die Herstellung von Monoalkylencar- bonaten, wie Ethylencarbonat oder Propylencarbonat. In den Beispielen der WO 84/03701 erfolgt bei 21 bar, DE-A 26 11 087 offenbart einen bevorzugten Bereich von 1 bis 30 Atmosphären.WO 84/03701 and DE-A 26 11 087 describe the preparation of monoalkylene carbonates, such as ethylene carbonate or propylene carbonate. In the examples of WO 84/03701 takes place at 21 bar, DE-A 26 11 087 discloses a preferred range of 1 to 30 atmospheres.

Gegenüber dem Stand der Technik ist ein Verfahren gewünscht, durch das bei einfacher Durchführung eine möglichst hohe Umsetzung der Alkylenoxidgruppen zu Alky- lencarbonatgruppen erreicht wird.Compared to the prior art, a method is desired by the simplest possible implementation of the highest possible conversion of the alkylene oxide is achieved to Alky- lencarbonatgruppen.

Aufgabe der vorliegenden Erfindung war, ein derartiges Verfahren zur Verfügung zu stellen.The object of the present invention was to provide such a method.

Demgemäß wurde das eingangs definierte Verfahren gefunden.Accordingly, the method defined above was found.

Bei dem erfindungsgemäßen Verfahren wird eine Verbindung mit mindestens zwei Alkylenoxidgruppen mit Kohlendioxid zu einer Verbindung mit mindestens zwei Alkylencarbonatgruppen umgesetzt. Das Kohlendioxid addiert sich dabei an die Alkyleno- xidgrupe unter Ausbildung der cyclischen Alkylencarbonatgruppe.In the process of the invention, a compound having at least two alkylene oxide groups is reacted with carbon dioxide to form a compound having at least two alkylene carbonate groups. The carbon dioxide is added to the alkylene oxide group to form the cyclic alkylene carbonate group.

Es kommen insbesondere Verbindungen mit 2 bis 4 Alkylenoxidgruppen in Betracht. Vorzugsweise handelt es sich um eine Verbindung mit zwei Alkylenoxidgruppen (kurz Bisalkylenoxid genannt), welche zu der entsprechenden Verbindung mit zwei Alkylen- carbonatgruppen (kurz Bisalkylencarbonat genannt) umgesetzt wird.In particular, compounds having 2 to 4 alkylene oxide groups are suitable. Preference is given to a compound having two alkylene oxide groups (abbreviated to bisalkylene oxide), which is converted to the corresponding compound having two alkylene carbonate groups (abbreviated to bisalkylene carbonate).

Besonders bevorzugt handelt es sich um eine Verbindung mit zwei Glyidylethergrup- pen, welche zu dem entsprechenden Bisalkylencarbonat der Formel IParticularly preferred is a compound having two Glyidylethergrup- pen, which to the corresponding Bisalkylencarbonat of formula I.

Figure imgf000003_0001
Figure imgf000003_0001

umgesetzt wird.is implemented.

Der Rest R in Formel I steht dabei für eine beliebige organische Gruppe mit 2 bis 30 C- Atomen, vorzugsweise 6 bis 30 C-Atomen und insbesondere 12 bis 24 C-Atomen.The radical R in formula I stands for any organic group having 2 to 30 C atoms, preferably 6 to 30 C atoms and in particular 12 to 24 C atoms.

Der Rest R kann neben Kohlenstoff- und Wasserstoffatomen auch Heteroatome wie Sauerstoff, Stickstoff und Schwefel enthalten. In einer bevorzugten Ausführungsform handelt es sich bei dem Rest R um eine Kohlenwasserstoffgruppe, welche keine Heteroatome enthält.In addition to carbon and hydrogen atoms, the radical R can also contain heteroatoms such as oxygen, nitrogen and sulfur. In a preferred embodiment, the radical R is a hydrocarbon group which contains no heteroatoms.

In einer besonders bevorzugten Ausführungsform steht R für eine Kohlenwasserstoffgruppe, welche mindestens eins, vorzugsweise ein oder zwei, besonders bevorzugt zwei aromatische Ringsysteme enthält. Als aromatisches Ringsystem sei insbesondere der Phenylring genannt.In a particularly preferred embodiment, R is a hydrocarbon group which contains at least one, preferably one or two, more preferably two aromatic ring systems. The aromatic ring system may be mentioned in particular the phenyl ring.

In einer besonderen Ausführungsform handelt es sich um zwei Phenylringe, die über eine Einfachbindung oder eine Kohlenwasserstoffgruppe verbunden sind; die Phenylringe können durch weitere Kohlenwasserstoffgruppen, insbesondere Alkylgruppen substituiert sein.In a particular embodiment, these are two phenyl rings joined via a single bond or a hydrocarbon group; the phenyl rings may be substituted by further hydrocarbon groups, in particular alkyl groups.

Ganz besonders bevorzugt handelt es sich bei dem Bisalkylencarbonat um denMost preferably, the bisalkylene carbonate is the

Bisphenol-A-bisglycerincarbonatylether der Formel Il (4,4'-((1-methylethylidene)bis(4,1- phenyleneoxymethylene))bis(1 ,3-dioxolan-2-one):Bisphenol A bisglycerol carbonyl ethers of the formula II (4,4 '- ((1-methylethylidenes) bis (4,1-phenyleneoxymethylene)) bis (1,3-dioxolan-2-ones):

Figure imgf000003_0002
Entsprechend handelt es sich bei der Ausgangsverbindung um den Bisphenol-A- bisglycidylether.
Figure imgf000003_0002
Accordingly, the starting compound is the bisphenol A bisglycidyl ether.

Die Umsetzung erfolgt erfindungsgemäß bei einem Druck von 12 bis 40 bar, vorzugsweise bei einem Druck von 12 bis 35 bar und besonders bevorzugt von 15 bis 30 bar, insbesondere 20 bis 30 bar.The reaction is carried out according to the invention at a pressure of 12 to 40 bar, preferably at a pressure of 12 to 35 bar and more preferably from 15 to 30 bar, in particular 20 to 30 bar.

Die Umsetzung erfolgt vorzugsweise bei einer Temperatur von 50 bis 1500C, besonders bevorzugt bei 60 bis 1000C und ganz besonders bevorzugt bei 70 bis 90°C.The reaction is preferably carried out at a temperature of 50 to 150 0 C, more preferably at 60 to 100 0 C and most preferably at 70 to 90 ° C.

Vorzugsweise erfolgt die Umsetzung in Gegenwart eines Lösemittels. Vorzugsweise wird das Lösemittel so gewählt, dass das Produkt der Umsetzung, z.B. das Bisalkylen- carbonat in dem Lösemittel nicht oder nur wenig löslich ist und daher als Feststoff aus der Reaktionslösung abgetrennt werden kann. Das Alkylencarbonat hat vorzugsweise bei 200C eine Löslichkeit in dem verwendeten Lösemittel von maximal 20 Gew.-Teile Alkylencarbonat, insbesondere maximal 10 Gew.-Teilen, besonders bevorzugt maximal 5 Gew.-Teilen Alkylencarbonat in 100 Gew.-Teilen Lösemittel. Geeignete Lösemittel sind insbesondere polare, aprotische Lösemittel z.B. Tetrahydro- furan oder Dialkylcarbonate. Besonders bevorzugte Lösemittel sind Dialkylcarbonate, ganz besonders bevorzugt Dimethylcarbonat.The reaction preferably takes place in the presence of a solvent. Preferably, the solvent is chosen so that the product of the reaction, for example the bisalkylene carbonate in the solvent is not or only slightly soluble and therefore can be separated as a solid from the reaction solution. The alkylene carbonate is preferably at 20 0 C a solubility in the solvent used of not more than 20 parts by weight alkylene carbonate, especially a maximum of 10 parts by weight, more preferably at most 5 parts by weight of alkylene carbonate in 100 parts by weight of solvent. Suitable solvents are, in particular, polar, aprotic solvents, for example tetrahydrofuran or dialkyl carbonates. Particularly preferred solvents are dialkyl carbonates, most preferably dimethyl carbonate.

Vorzugsweise wird die Umsetzung in Gegenwart eines Katalysators durchgeführt.Preferably, the reaction is carried out in the presence of a catalyst.

Als Katalysatoren kommen z.B. Phosphorverbindungen mit einem dreiwertigen Phosphoratom, z.B. tertiäre Phosphine wie Trialkyl- oder Triarylphosphin, oder Salze von quaternären Ammoniumverbindungen in Betracht.As catalysts are e.g. Phosphorus compounds having a trivalent phosphorus atom, e.g. tertiary phosphines such as trialkyl or triarylphosphine, or salts of quaternary ammonium compounds into consideration.

Als Salze der quaternäre Ammoniumverbindungen bevorzugt sind solche der FormelPreferred salts of the quaternary ammonium compounds are those of the formula

RaRbRcRd N+ Y-,RaRbRcRd N + Y-,

worin Ra , Rb, Rc und Rd unabhängig voneinander für eine Kohlenwasserstoffgruppe mit 1 bis 12 C-Atomen, z.B. eine Alkyl- oder Arylgruppe, stehen und Y" für ein Anion, insbesondere ein Halogenid, besonders bevorzugt ein Chlorid steht.wherein R a , Rb, Rc and Rd independently represent a hydrocarbon group having 1 to 12 C-atoms, for example an alkyl or aryl group, and Y "is an anion, in particular a halide, particularly preferably a chloride.

Bevorzugte Salze der quaternären Ammoniumverbindungen sind die Halogenide, insbesondere Chloride und Bromide.Preferred salts of the quaternary ammonium compounds are the halides, especially chlorides and bromides.

Genannt seien z.B. Benzyltrimethylammoniumchlorid oder Tetraethylammoniumbro- mid. In einer besonderen Ausführungsform kann das vorstehende Salz der quaternären Ammoniumverbindung in Kombination mit einem Metallsalz verwendet werden. Als Metallsalz kommen z.B. Metallhalogenide wie Alkalichloride, Alkalibromide, Alkaliiodi- de, Zinkhalogenide in betracht. Genannt seien z.B. Kaliumjodid und ZnBr2.Examples include benzyltrimethylammonium chloride or tetraethylammonium bromide. In a particular embodiment, the above salt of the quaternary ammonium compound may be used in combination with a metal salt. As a metal salt, for example, metal halides such as alkali metal chlorides, alkali bromides, Alkaliiodi- de, zinc halides considered. Examples include potassium iodide and ZnBr2.

Die Menge der verwendeten Katalysatoren beträgt vorzugsweise mindestens 0,1 Gewichtsteil, besonders bevorzugt mindestens 0,3 Gewichtsteile und ganz besonders bevorzugt mindestens 0,5 Gewichtsteile auf 100 Gewichtsteile Alkylenoxid. Die Menge der verwendeten Katalysatoren beträgt vorzugsweise nicht mehr als 20 Gewichtsteile, besonders bevorzugt nicht mehr als 15 Gewichtsteile auf 100 Gewichtsteile Alkylenoxid. Im Allgemeinen ist ein Gehalt zwischen 0,5 und 10 Gewichtsteilen auf 100 Gewichtsteile Alkylenoxid ausreichend.The amount of the catalysts used is preferably at least 0.1 part by weight, more preferably at least 0.3 part by weight and most preferably at least 0.5 part by weight per 100 parts by weight of alkylene oxide. The amount of the catalysts used is preferably not more than 20 parts by weight, more preferably not more than 15 parts by weight per 100 parts by weight of alkylene oxide. In general, a content of between 0.5 and 10 parts by weight per 100 parts by weight of alkylene oxide is sufficient.

Die Durchführung der Umsetzung kann in üblicher weise in einem Autoklaven erfolgen.The implementation of the reaction can be carried out in a conventional manner in an autoclave.

Die Ausgangsverbindungen, d.h. das Alkylenoxid, Lösemittel und Katalysator können im Autoklaven vorgelegt werden und anschließend wird durch Einleiten des gasförmigen Kohlendioxid der gewünschte Druck eingestellt.The starting compounds, i. the alkylene oxide, solvent and catalyst can be placed in the autoclave and then the desired pressure is set by introducing the gaseous carbon dioxide.

Das entstehende Alkylencarbonat fällt aus der Reaktionslösung als Feststoff aus und kann nach beendeter Reaktion in einfacher Weise abgetrennt werden.The resulting alkylene carbonate precipitates out of the reaction solution as a solid and can be easily separated after completion of the reaction.

Das erhaltene Produkt kann gegebenenfalls Verbindungen enthalten, in denen nicht alle Alkylenoxidgruppen in Alkylencarbonatgruppen umgewandelt wurden. Es ist jedoch ein Vorteil der Erfindung, dass die Umsetzung sehr einfach und nahezu vollständig verläuft, so dass mehr als 70 mol%, insbesondere mehr als 85 mol % ganz besonders bevorzugt mehr als 90 mol % aller Alkylenoxidgruppen in Alkylencarbonatgruppen umgewandelt sind.The product obtained may optionally contain compounds in which not all alkylene oxide groups have been converted to alkylene carbonate groups. However, it is an advantage of the invention that the reaction is very simple and almost complete, so that more than 70 mol%, in particular more than 85 mol%, very particularly preferably more than 90 mol% of all alkylene oxide groups are converted into alkylene carbonate groups.

Die Epoxyzahl des erhaltenen Produkts ist vorzugsweise größer 2000 und besonders bevorzugt größer 3000. Die Epoxyzahl ist der Quotient aus der Masse des Produkts in Gramm und der Molzahl der vorhandenen Epoxygruppen. Die Epoxyzahl ist umso größer, je geringer die Anzahl der noch verbliebenen Epoxygrupen ist.The epoxy number of the product obtained is preferably greater than 2000 and more preferably greater than 3000. The epoxy number is the quotient of the mass of the product in grams and the number of moles of epoxy groups present. The lower the number of remaining epoxy groups, the greater the epoxy number.

Das erhaltene Alkylencarbonat, insbesondere Bisalkylencarbonat, eignet sich als Bestandteil eines zweikomponentigen (2-K) Systems. Die eine Komponente (1. Komponente) ist das Alkylencarbonat, insbesondere Bisalkylencarbonat, allein oder gegebenenfalls im Gemisch mit weiteren Verbindungen, die andere (2.) Komponente ist vorzugsweise eine Aminoverbindung oder Gemisch von Aminoverbindungen. Das 2- K-system kann z.B. als Lack- oder Klebstoff System oder zur Herstellung von Composi- tes verwendet werden. Als 2. Komponente in Betracht kommen insbesondere Aminoverbindungen mit mindestens zwei Aminogruppen, wobei es sich um sekundäre oder primäre Aminogruppen handeln kann. Bevorzugte Verbindungen mit zwei sekundären Aminogruppen sind ins- besondere cyclische Verbindungen wie Piperazin. Besonders bevorzugt sind Aminoverbindungen mit mindestens zwei primären Aminogruppen. Die beiden Komponenten werden üblicherweise erst kurz vor ihrer Verwendung zusammengegeben. Bei Aminoverbindungen mit mehr zwei primären Aminogruppen und einem Bisalkylencarbonat werden vernetzte Polymersysteme erhalten. Ein derartiges 2-K-System stellt eine Al- ternative zu Epoxy- oder PU-Systemen dar.The resulting alkylene carbonate, in particular bisalkylene carbonate, is suitable as part of a two-component (2-K) system. The one component (1st component) is the alkylene carbonate, in particular bisalkylene carbonate, alone or optionally in admixture with other compounds, the other (2.) component is preferably an amino compound or mixture of amino compounds. The 2-component system can be used, for example, as a paint or adhesive system or for the production of composites. In particular, amino compounds having at least two amino groups, which may be secondary or primary amino groups, are suitable as the second component. Preferred compounds having two secondary amino groups are in particular cyclic compounds such as piperazine. Particularly preferred are amino compounds having at least two primary amino groups. The two components are usually combined just before use. For amino compounds having more than two primary amino groups and a bisalkylene carbonate, crosslinked polymer systems are obtained. Such a 2-component system represents an alternative to epoxy or PU systems.

In einer weiteren Verwendungsform kann das Alkylencarbonat, insbesondere Bisalkylencarbonat zunächst mit einer Aminoverbindung mit mindestens zwei primären oder sekundären Aminogruppen umgesetzt werden. Bevorzugte Verbindungen mit zwei sekundären Aminogruppen sind wiederum cyclische Verbindungen wie Piperazin. Besonders bevorzugt sind Aminoverbindungen mit mindestens zwei primären Aminogruppen. Bevorzugt liegen die Aminogruppen im Verhältnis zu den Carbonatgruppen im Überschuss vor. Vorzugsweise beträgt das Molverhältnis der primären Aminogruppen zu den Carbonatgruppen 2 : 1 ; z.B. werden auf 1 Mol Bisalkylencarbonat zwei Mol Diamin eingesetzt. Das erhaltene Reaktionsprodukt hat dann die entsprechende Anzahl von freien, reaktiven Aminogruppen und eignet sich als Aminhärter für Epoxyhar- ze.In a further use form, the alkylene carbonate, in particular bisalkylene carbonate, can first be reacted with an amino compound having at least two primary or secondary amino groups. Preferred compounds having two secondary amino groups are in turn cyclic compounds such as piperazine. Particularly preferred are amino compounds having at least two primary amino groups. The amino groups are preferably present in excess in relation to the carbonate groups. Preferably, the molar ratio of the primary amino groups to the carbonate groups is 2: 1; e.g. Two moles of diamine are used per mole of bisalkylene carbonate. The resulting reaction product then has the corresponding number of free, reactive amino groups and is suitable as an amine hardener for epoxy resins.

BeispieleExamples

In einem Metallautoklaven (270 Milliliter) wurden 40 g (1 18 mmol) Bisphenol-A- bisglyidylether (BGE) in 80 Milliliter Dimethylcarbonat (DMC) vorgelegt und mit 2,16 g (1 1 ,0 mmol) Benzyltrimethylammoniumchlorid (BTMACI, 98%-ig) sowie 3,41 g (15 mmol) Zinkbromid (ZnBr2 , 98%-ig) oder 2,5 g (15 mmol) KJ versetzt. Das Reaktionsgemisch wurde auf 800C erhitzt und der Druck durch Aufpressen von CO2 eingestellt. Der nach der Umsetzung entstandene farblose, wasserunlösliche Feststoff wurde mit Wasser gewaschen und im Vakuum getrocknet. Man erhält BGE-Carbonat als farblosen Feststoff (Schmelzpunkt 148 bis 1500C), gegebenenfalls im Gemisch mit nicht - umgesetztem Edukt. Maß für die Überführung von Glycidylgruppen in Carbonatgruppen ist die Epoxyzahl (Masse Produkte/Mol Epoxygruppen); je höher die Epoxyzahl, desto geringer ist der Gehalt an Epoxygruppen. Die Epoxyzahl wurde gemäß DIN Norm ASTM D 1652 bestimmt. In a metal autoclave (270 milliliters), 40 g (1 18 mmol) of bisphenol A bisglyidyl ether (BGE) in 80 milliliters of dimethyl carbonate (DMC) and 2.16 g (1 1, 0 mmol) of benzyltrimethylammonium chloride (BTMACI, 98%). -ig) and 3.41 g (15 mmol) of zinc bromide (ZnBr 2 , 98% strength) or 2.5 g (15 mmol) of KI. The reaction mixture was heated to 80 ° C. and the pressure was adjusted by pressing in CO 2 . The colorless, water-insoluble solid formed after the reaction was washed with water and dried in vacuo. BGE carbonate is obtained as a colorless solid (melting point 148 to 150 ° C.), if appropriate mixed with unreacted educt. A measure of the conversion of glycidyl groups into carbonate groups is the epoxy number (mass of products / mole of epoxy groups); the higher the epoxy number, the lower the content of epoxy groups. The epoxy number was determined according to DIN standard ASTM D 1652.

Figure imgf000007_0001
ie mit V gekennzeichneten Beispiele sind Vergleichsbeispiele.
Figure imgf000007_0001
The examples marked V are comparative examples.

Claims

Patentansprüche Patent claims 1. Verfahren zur Herstellung von Verbindungen mit mindestens zwei Alkylencarbo- natgruppen (kurz Alkylencarbonat genannt) durch Umsetzung einer Verbindung mit mindestens zwei Alkylenoxidgruppen (kurz Alkylenoxid genannt) mit Kohlendioxid, dadurch gekennzeichnet, dass die Umsetzung bei einem Druck von 12 bis 40 bar erfolgt.1. A process for producing compounds with at least two alkylene carbonate groups (called alkylene carbonate for short) by reacting a compound with at least two alkylene oxide groups (called alkylene oxide for short) with carbon dioxide, characterized in that the reaction takes place at a pressure of 12 to 40 bar. 2. Verfahren gemäß Anspruch 1 , dadurch gekennzeichnet, dass eine Verbindung mit zwei Alkylenoxidgruppen (kurz Bisalkylenoxid genannt) zur entsprechenden2. The method according to claim 1, characterized in that a compound with two alkylene oxide groups (called bisalkylene oxide for short) to the corresponding Verbindung mit zwei Alkylencarbonatgruppen (kurz Bisalkylencarbonat genannt) umgesetzt wird.Compound with two alkylene carbonate groups (called bisalkylene carbonate for short) is implemented. 3. Verfahren gemäß Anspruch 1 oder 2, dadurch gekennzeichnet, dass es sich bei dem Bisalkylencarbonat um eine Verbindung der Formel I3. The method according to claim 1 or 2, characterized in that the bisalkylene carbonate is a compound of the formula I
Figure imgf000008_0001
Figure imgf000008_0001
 handelt, worin R für eine organische Gruppe mit 2 bis 30 C-Atomen steht.is where R represents an organic group with 2 to 30 carbon atoms. 4. Verfahren gemäß einem der Ansprüche 1 bis 3, dadurch gekennzeichnet, dass es sich bei dem Alkylencarbonat um den Bisphenol-A-bisglycerincarbonatylether der Formel Il4. The method according to any one of claims 1 to 3, characterized in that the alkylene carbonate is the bisphenol A bisglycerol carbonateyl ether of the formula II
Figure imgf000008_0002
Figure imgf000008_0002
 handelt.acts. 5. Verfahren gemäß einem der Ansprüche 1 bis 4, dadurch gekennzeichnet, dass die Umsetzung in einem Lösemittel durchgeführt wird, in dem bei 200C maximal 20 Gew.-Teile Alkylencarbonat in 100 Gew.-Teilen Lösemittel löslich sind. 5. The method according to any one of claims 1 to 4, characterized in that the reaction is carried out in a solvent in which a maximum of 20 parts by weight of alkylene carbonate are soluble in 100 parts by weight of solvent at 20 0 C. 6. Verfahren gemäß einem der Ansprüche 1 bis 5, dadurch gekennzeichnet, dass die Umsetzung in einem Dialkylcarbonat, vorzugsweise Dimethylcarbonat, als Lösemittel durchgeführt wird.6. The method according to any one of claims 1 to 5, characterized in that the reaction is carried out in a dialkyl carbonate, preferably dimethyl carbonate, as a solvent. 7. Verfahren gemäß einem der Ansprüche 1 bis 6, dadurch gekennzeichnet, dass das Alkylencarbonat als Feststoff aus der Reaktionslösung abgetrennt wird.7. The method according to any one of claims 1 to 6, characterized in that the alkylene carbonate is separated off as a solid from the reaction solution. 8. Verfahren gemäß einem der Ansprüche 1 bis 7, dadurch gekennzeichnet, dass das Reaktionsprodukt eine Epoxyzahl größer 2000 hat.8. The method according to any one of claims 1 to 7, characterized in that the reaction product has an epoxy number greater than 2000. 9. Verfahren gemäß einem der Ansprüche 1 bis 8, dadurch gekennzeichnet, dass das erhaltene Alkylencarbonat, insbesondere Bisalkylencarbonat, als Bestandteil eines zweikomponentigen (2-K) Systems verwendet wird, wobei die9. The method according to any one of claims 1 to 8, characterized in that the alkylene carbonate obtained, in particular bisalkylene carbonate, is used as a component of a two-component (2-K) system, wherein the 2. Komponente eine Aminoverbindung ist.2nd component is an amino compound. 10. Verfahren gemäß einem der Ansprüche 1 bis 8, dadurch gekennzeichnet, dass das erhaltene Alkylencarbonat als Bestandteil eines zweikomponentigen Lackoder Klebstoffsystems (2-K-System) oder eines 2 K-Systems zur Herstellung von Composites verwendet wird.10. The method according to any one of claims 1 to 8, characterized in that the alkylene carbonate obtained is used as a component of a two-component paint or adhesive system (2-K system) or a 2-K system for the production of composites. 1 1. Verfahren gemäß einem der Ansprüche 1 bis 8, dadurch gekennzeichnet, dass das erhaltene Alkylencarbonat anschließend mit einem Überschuss einer Aminoverbindung umgesetzt wird und die erhaltene Verbindung als Aminhärter in 2-K- Systemen verwendet wird. 1 1. The method according to any one of claims 1 to 8, characterized in that the alkylene carbonate obtained is then reacted with an excess of an amino compound and the compound obtained is used as an amine hardener in 2-K systems.
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