EP0927216A1 - Process for preparing polymers with recurring succinyl units - Google Patents

Process for preparing polymers with recurring succinyl units

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Publication number
EP0927216A1
EP0927216A1 EP97940126A EP97940126A EP0927216A1 EP 0927216 A1 EP0927216 A1 EP 0927216A1 EP 97940126 A EP97940126 A EP 97940126A EP 97940126 A EP97940126 A EP 97940126A EP 0927216 A1 EP0927216 A1 EP 0927216A1
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EP
European Patent Office
Prior art keywords
ammonia
acid
reaction
maleic anhydride
polymerization
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.)
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Application number
EP97940126A
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German (de)
French (fr)
Inventor
Paul Wagner
Frank Döbert
Torsten Groth
Winfried Joentgen
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Bayer AG
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Bayer AG
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Publication of EP0927216A1 publication Critical patent/EP0927216A1/en
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C227/00—Preparation of compounds containing amino and carboxyl groups bound to the same carbon skeleton
    • C07C227/04—Formation of amino groups in compounds containing carboxyl groups
    • C07C227/06—Formation of amino groups in compounds containing carboxyl groups by addition or substitution reactions, without increasing the number of carbon atoms in the carbon skeleton of the acid
    • C07C227/08—Formation of amino groups in compounds containing carboxyl groups by addition or substitution reactions, without increasing the number of carbon atoms in the carbon skeleton of the acid by reaction of ammonia or amines with acids containing functional groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C231/00—Preparation of carboxylic acid amides
    • C07C231/02—Preparation of carboxylic acid amides from carboxylic acids or from esters, anhydrides, or halides thereof by reaction with ammonia or amines
    • 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
    • C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
    • C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
    • C08G69/08—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from amino-carboxylic acids
    • C08G69/10—Alpha-amino-carboxylic 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
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/0605—Polycondensates containing five-membered rings, not condensed with other rings, with nitrogen atoms as the only ring hetero atoms
    • C08G73/0611—Polycondensates containing five-membered rings, not condensed with other rings, with nitrogen atoms as the only ring hetero atoms with only one nitrogen atom in the ring, e.g. polypyrroles

Definitions

  • the invention relates to a process for the preparation of polymers with recurring succinyl units.
  • PAA polyaspartic acid
  • US-A 5 288 783 describes the production of PSI from maleic anhydride and ammonia at higher temperatures and the hydrolysis to PAA.
  • DE-A 43 00 020 covers the production of polymers of aspartic acid by thermal condensation of half-amides of maleic acid, fumaric acid or of ammonium salts of half-amides. The reaction takes place at temperatures above the melting point of maleic anhydride with gaseous ammonia.
  • the present invention relates to a process for the preparation of polymers with recurring succinyl units, characterized in that maleic acid anhydride, maleic acid and / or fumaric acid, optionally in the presence of
  • Comonomers are reacted with condensed liquid ammonia and the reaction product obtained is polymerized and optionally hydrolyzed.
  • the conversion of, for example, maleic anhydride into liquid ammonia can be carried out, boiling cooling by means of evaporating ammonia being able to be used as a simple and efficient method for temperature control.
  • the polymers produced according to the invention preferably have recycle
  • iminodissucinate units can preferably be contained in at least one of the following structures:
  • the polymer produced preferably shows chain lengths or molecular weights according to gel permeation chromatography analyzes (Mw) of 500 to 10,000, preferably 500 to 5,000, particularly preferably 700 to 4,500. Based on the groups
  • (recurring aspartic acid units) preferably have at least 50%, in particular at least 70%, ⁇ -linked.
  • iminodisuccinate units are present, they can be randomly distributed in the polymer or preferably present as an end group. Based on the sum of all recurring units, the iminodisuccinate unit is present in a preferred embodiment in at least 0.1 mol%.
  • the molar ratio of the iminodisuccinate units incorporated in the polymer to the sum of all monomer units incorporated in the polymer is preferably 0.1 mol% to 99 mol%, preferably 1 mol% to 50 mol%, particularly preferably 2 mol% to 25 Mole%.
  • the starting materials can be used individually or in mixtures, in bulk or in solution.
  • the polymers according to the invention can optionally be present as a free acid or as a salt, preferred salts are e.g. Alkali and
  • maleic anhydride or its derivatives are used as a melt.
  • the reaction of the starting materials can optionally be carried out in the presence of a colsolvent.
  • a colsolvent lower alcohols, polar aprotic solvents such as dimethylformamide, N-alkylpyrrolidones, sulfolane, acetone, polyalkylene glycols, polyalkylene glycol monoalkyl ethers and polyalkylene glycol dialkyl ethers are suitable as cosolvents.
  • Supercritical gases such as e.g. Carbon dioxide.
  • the starting materials are molten maleic anhydride and ammonia.
  • Molten maleic anhydride is preferably introduced into a reactor filled with liquid ammonia.
  • the temperature of the maleic anhydride is 60 to 100 ° C.
  • the reaction of the maleic anhydride preferably takes place at temperatures between 60 and 100 ° C and a pressure of 26 to 64 bar.
  • the molar ratio of maleic anhydride and ammonia is preferably at least 1: 4, it is preferably 1: 4 to 1: 500.
  • the excess of ammonia is of particular advantage since the reaction of the anhydride with the ammonia is a very fast and highly exothermic reaction. By evaporating ammonia, the heat of reaction can be easily dissipated without additional diluents. Due to the excess
  • ammonia can form the ammonium salt of maleic acid.
  • intermediate products such as maleic acid diammonium salt or maleic acid ammonium salt can be prepared from the starting materials mentioned above in a separate process step and then thermally polymerized batchwise or continuously in bulk or in suitable solvents.
  • the invention therefore also relates to a process for the preparation of unpolymerized nitrogen compounds of a C, -carboxylic acid, characterized in that maleic anhydride, maleic acid and / or fumaric acid are reacted with condensed liquid ammonia to give a low molecular weight product.
  • This can be, for example, an amide, imide or ammonium salt, in particular the mono- or diammonium salt of maleic acid, maleic acid, aspartic acid, iminodisuccinic acid, iminodisuccinamic acids or asparagine.
  • the polymerization of the reaction product is generally carried out at temperatures between 100 ° C. and 350 ° C., preferably between 120 ° C. and 250 ° C., particularly preferably between 120 ° C. and 220 ° C.
  • the residence time is preferably between 1 second and 600 minutes, preferably 5 seconds to 180 minutes, particularly preferably 10 seconds to 150 minutes. However, it can also be done differently, e.g. with microwaves.
  • all apparatus are suitable for thermal polymerization which, with a narrow residence time distribution, permit the necessary minimum residence time for the polymerization and at the same time an at least partial evaporation of the solvent and of the water formed during the reaction.
  • Preferred devices for thermal polymerization are therefore all apparatuses which have a defined residence time with a narrow residence time distribution for the solid or highly viscous phase and at the same time good temperature control by at least partial evaporation of the solvent (organic solvent and / or water) and / or enable the water of reaction formed in the polymerization.
  • solvent organic solvent and / or water
  • Such preferred devices can be, for example
  • Suitable bases are alkali and alkaline earth metal hydroxides or carbonates such as sodium hydroxide solution, potassium hydroxide solution, sodium carbonate or potassium carbonate, ammonia and amines such as triethylamine, triethanolamine, diethylamine, diethanolamine, alkylamines etc.
  • the temperature during the hydrolysis is preferably in a range including up to the boiling point of the suspension or solution containing succinyl groups and preferably at 20 to 150 ° C.
  • the hydrolysis is optionally carried out under pressure.
  • the hydrolysis is optionally carried out with the addition of a further monoethylenically unsaturated carboxylic acid derivative.
  • a further monoethylenically unsaturated carboxylic acid derivative for example, maleic anhydride, maleic acid, citraconic acid, itaconic acid, aconitic acid, acrylic acid and fumaric acid are suitable.
  • the amino groups of the N-terminal end of the polymer molecule can be added to the monoethylenically unsaturated carboxylic acid derivative present in the salt form.
  • the primary polymerization products can also have ethylenically unsaturated end groups. It may therefore be useful to optionally add aminocarboxylic acids to the reaction mixture during the basic hydrolysis, e.g. Glycine, aspartic acid, lysine,
  • Glutamic acid etc. for example also add ammonia.
  • a grafting of the polymer end groups is achieved by this measure.
  • the polymers are characterized by an improved calcium binding process. Furthermore, they show complexing properties compared to heavy metals such as copper, iron etc. They can be used as additives in phosphate-free and phosphate-free detergents and cleaning agents.
  • the polymers are builders for detergents and reduce the incrustation and graying on the washed fabric during the washing process. Furthermore, the polymers according to the invention inhibit and delay the precipitation of salts, in particular crystals, for example calcium carbonate, calcium sulfate, calcium phosphate, barium sulfate and magnesium silicate, from aqueous solutions and are therefore suitable as water treatment agents. They can be added to the water in cooling circuits, evaporators or seawater desalination plants and pressurized water for secondary oil production and water treatment in mining. They can also be used as deposit inhibitors when evaporating sugar juice.
  • the copolymers can also serve as stabilizers for bleaching agents such as hydrogen peroxide in bleaching processes.
  • copolymers according to the invention are to be classified as biodegradable according to the "OECD Guidelines for testing of chemicals (1981)".
  • Yield of the sodium salt of polyaspartic acid was 123 g.
  • the weight average molecular weight determined by means of gel permeation chromatography was approx. 1750 g / mol, the ß fraction approx. 70%.

Abstract

Polymers with recurring succinyl units are prepared by reacting maleic acid anhydride, maleic acid or fumaric acid with condensed liquid ammonia and polymerizing the resultant reaction product.

Description

Verfahren zur Herstellung von Polymeren mit wiederkehrenden Succinyl- einheitenProcess for the preparation of polymers with recurring succinyl units
Die Erfindung betrifft ein Verfahren zur Herstellung von Polymeren mit wiederkehrenden Succinyleinheiten.The invention relates to a process for the preparation of polymers with recurring succinyl units.
Die Herstellung und Verwendung von Polyasparaginsäure (PAA) und ihrer Derivate ist seit langem Gegenstand zahlreicher Veröffentlichungen und Patente.The production and use of polyaspartic acid (PAA) and its derivatives has long been the subject of numerous publications and patents.
Gemäß J. Org. Chem., 24, p. 1662-1666, (1959), wird Polysuccinimid (PSI), welches dort als "Anhydropolyasparaginsäure" bezeichnet wird, durch thermischeAccording to J. Org. Chem., 24, p. 1662-1666, (1959), polysuccinimide (PSI), which is referred to there as "anhydropolyaspartic acid", by thermal
Polykondensation von Maleinamidsäure oder Äpfelsäuremonoammoniumsalz bei Temperaturen bis 200°C erhalten. Die Polymerausbeuten betrugen bei 200°C 75 % bis 79 %. Weiterhin werden als mögliche Einsatzstoffe Äpfelsäure, Maleinsäureanhydrid, Fumarsäure und Asparagin genannt.Polycondensation of maleic acid or malic acid monoammonium salt obtained at temperatures up to 200 ° C. The polymer yields were 75% to 79% at 200 ° C. Malic acid, maleic anhydride, fumaric acid and asparagine are also mentioned as possible starting materials.
US-A 4 839 461 (= EP-A 0 256 366) beschreibt die Herstellung von Polyasparaginsäure aus Maleinsäureanhydrid, Wasser und Ammoniak. Maleinsäureanhydrid wird im wäßrigen Medium unter Zugabe von konzentrierter Ammoniaklösung umgesetzt und anschließend polymerisiert. US-A 5 288 783 beschreibt die Herstellung von PSI aus Maleinsäureanhydrid und Ammoniak bei höheren Temperaturen und die Hydrolyse zu PAA.US-A 4 839 461 (= EP-A 0 256 366) describes the preparation of polyaspartic acid from maleic anhydride, water and ammonia. Maleic anhydride is reacted in an aqueous medium with the addition of concentrated ammonia solution and then polymerized. US-A 5 288 783 describes the production of PSI from maleic anhydride and ammonia at higher temperatures and the hydrolysis to PAA.
DE-A 43 00 020 umfaßt die Herstellung von Polymerisaten der Asparaginsäure durch thermische Kondensation von Halbamiden der Maleinsäure, Fumarsäure oder von Ammoniumsalzen der Halbamide. Die Umsetzung erfolgt bei Temperaturen oberhalb des Schmelzpunktes von Maleinsäureanhydrid mit gasförmigem Ammoniak.DE-A 43 00 020 covers the production of polymers of aspartic acid by thermal condensation of half-amides of maleic acid, fumaric acid or of ammonium salts of half-amides. The reaction takes place at temperatures above the melting point of maleic anhydride with gaseous ammonia.
Nachteilig an den bekannten Verfahren ist u.a., daß die Entfernung des Wassers im Polymerisationsschritt Schwierigkeiten bereiten kann.One disadvantage of the known processes is that the removal of the water in the polymerization step can be difficult.
Die vorliegende Erfindung betrifft ein Verfahren zur Herstellung von Polymeren mit wiederkehrenden Succinyleinheiten, dadurch gekennzeichnet, daß Maleinsäurc- anhydrid, Maleinsäure und/oder Fumarsäure, gegebenenfalls in Gegenwart vonThe present invention relates to a process for the preparation of polymers with recurring succinyl units, characterized in that maleic acid anhydride, maleic acid and / or fumaric acid, optionally in the presence of
Comonomeren, mit kondensiertem flüssigem Ammoniak umgesetzt werden und das erhaltene Reaktionsprodukt polymerisiert und gegebenenfalls hydrolysiert wird. Überraschenderweise kann die Umsetzung von beispielsweise Maleinsäureanhydrid in flüssigem Ammoniak durchgeführt werden, wobei die Siedekühlung durch verdampfendes Ammoniak als eine einfache und effiziente Methode zur Temperaturkontrolle genutzt werden kann.Comonomers are reacted with condensed liquid ammonia and the reaction product obtained is polymerized and optionally hydrolyzed. Surprisingly, the conversion of, for example, maleic anhydride into liquid ammonia can be carried out, boiling cooling by means of evaporating ammonia being able to be used as a simple and efficient method for temperature control.
Die erfmdungsgemäß hergestellten Polymere weisen vorzugsweise wiederkelirendeThe polymers produced according to the invention preferably have recycle
Succinyl-Einheiten mit wenigstens einer der folgenden Strukturen aufSuccinyl units with at least one of the following structures
CH — CO-N— — CH-CO- N —CH - CO-N— - CH-CO- N -
| ' , und | I , bevorzugt| ', and | I, preferred
CH — CO- CH2- CO-CH - CO- CH 2 - CO-
CH; CO CH: CO — NH- -CH - CO — NH-CH; CO CH: CO - NH- -CH - CO - NH-
I /N ~ •CH CO — CH COOH CH2 COOHI / N ~ • CH CO - CH COOH CH 2 COOH
ß-Form α-Formβ-form α-form
CH •CO — NH - — CH CO — NH-CH • CO - NH - - CH CO - NH-
•CH CO- NH2 CH2 CO-NH2 • CH CO-NH 2 CH 2 CO-NH 2
oder eines Salzes davon.or a salt thereof.
Zusätzlich können Iminodissucinateinheiten in vorzugsweise wenigstens einen der folgenden Strukturen enthalten sein:In addition, iminodissucinate units can preferably be contained in at least one of the following structures:
wobei R OH, O'NH oder NH, bedeutet. Das hergestellte Polymer zeigt in Abhängigkeit von den Reaktionsbedingungen, beispielsweise Verweilzeit und Temperatur der thermischen Polymerisation, vorzugsweise Kettenlängen bzw. Molekulargewichte nach gelpermeationschromatogra- phischen Analysen (Mw) von 500 bis 10.000, bevorzugt 500 bis 5.000, besonders bevorzugt 700 bis 4.500. Bezogen auf die Gruppen where R is OH, O ' NH or NH. Depending on the reaction conditions, for example residence time and temperature of the thermal polymerization, the polymer produced preferably shows chain lengths or molecular weights according to gel permeation chromatography analyzes (Mw) of 500 to 10,000, preferably 500 to 5,000, particularly preferably 700 to 4,500. Based on the groups
CH, CO-NH — CH - • CO-NH-CH, CO-NH - CH - • CO-NH-
I und II and I
CH - COOH CH- -COOHCH - COOH CH - COOH
ß-Form α-Formβ-form α-form
(wiederkehrende Asparaginsäureeinheiten) Hegen vorzugsweise wenigstens 50%, insbesondere wenigstens 70%, ß-verknüpft vor.(recurring aspartic acid units) preferably have at least 50%, in particular at least 70%, β-linked.
Soweit Iminodisuccinateinheiten vorliegen, können sie im Polymer statistisch verteilt oder bevorzugt als Endgruppe vorliegen. Bezogen auf die Summe aller wiederkehrenden Einheiten liegt die Iminodisuccinateinheit in einer bevorzugten Ausführungsform zu wenigstens 0,1 Mol-% vor. Das molare Verhältnis der im Polymer eingebauten Iminodisuccinateinheiten zur Summe aller im Polymer einge- bauten Monomereinheiten beträgt vorzugsweise 0,1 Mol-% bis 99 Mol-%, bevorzugt 1 Mol-% bis 50 Mol-%, besonders bevorzugt 2 Mol-% bis 25 Mol-%.If iminodisuccinate units are present, they can be randomly distributed in the polymer or preferably present as an end group. Based on the sum of all recurring units, the iminodisuccinate unit is present in a preferred embodiment in at least 0.1 mol%. The molar ratio of the iminodisuccinate units incorporated in the polymer to the sum of all monomer units incorporated in the polymer is preferably 0.1 mol% to 99 mol%, preferably 1 mol% to 50 mol%, particularly preferably 2 mol% to 25 Mole%.
Zusätzlich können durch geeignete Reaktionsführung und Wahl der Edukte weitere wiederkehrende Einheiten enthalten sein, z. B.In addition, further recurring units can be contained by suitable reaction control and choice of the starting materials, e.g. B.
a) Äpfelsäure-Einheiten der Formela) Malic acid units of the formula
b) Maleinsäure- und Fumarsäure-Einheiten der Formel b) Maleic acid and fumaric acid units of the formula
Die Edukte können einzeln oder in Gemischen, in Substanz oder in Lösung, eingesetzt werden. Die erfindungsgemäßen Polymeren können gegebenenfalls als freie Säure oder als Salz vorliegen, bevorzugte Salze sind z.B. Alkali- undThe starting materials can be used individually or in mixtures, in bulk or in solution. The polymers according to the invention can optionally be present as a free acid or as a salt, preferred salts are e.g. Alkali and
Ammoniumsalze.Ammonium salts.
Maleinsäureanhydrid oder ihre Derivate werden in einer bevorzugten Λusfüh- rungsform als Schmelze eingesetzt.In a preferred embodiment, maleic anhydride or its derivatives are used as a melt.
Die Umsetzung der Edukte kann gegebenenfalls in Gegenwart eines Colsolvens durchgeführt werden. Als Cosolvens geeignet sind niedere Alkohole, polar apro- tische Lösungsmittel, wie Dimethylformamid, N-Alkylpyrrolidone, Sulfolan, Ace- ton, Polyalkylenglykole, Polyalkylenglykolmonoalkylether und Polyalkylenglykol- dialkylether. Ebenfalls geeignet sind überkritische Gase, wie z.B. Kohlendioxid.The reaction of the starting materials can optionally be carried out in the presence of a colsolvent. Lower alcohols, polar aprotic solvents such as dimethylformamide, N-alkylpyrrolidones, sulfolane, acetone, polyalkylene glycols, polyalkylene glycol monoalkyl ethers and polyalkylene glycol dialkyl ethers are suitable as cosolvents. Supercritical gases such as e.g. Carbon dioxide.
In einer bevorzugten Ausführungsform sind die Edukte geschmolzenes Malein- säureanhydrid und Ammoniak.In a preferred embodiment, the starting materials are molten maleic anhydride and ammonia.
Vorzugsweise leitet man geschmolzenes Maleinsäureanhydrid in einen mit flüssigem Ammoniak gefüllten Reaktor ein. Die Temperatur des Maleinsäureanhydrids beträgt hierbei 60 bis 100°C. Die Umsetzung des Maleinsäureanhydrids findet bevorzugt bei Temperaturen zwischen 60 und 100°C und einem Druck von 26 bis 64 bar statt. Das molare Verhältnis von Maleinsäureanhydrid und Ammoniak ist bevorzugt wenigstens 1 :4, es beträgt bevorzugt 1 :4 bis 1 :500. Der Überschuß an Ammoniak ist von besonderem Vorteil, da die Umsetzung des Anhydrids mit dem Ammoniak eine sehr schnelle und stark exotherme Reaktion ist. Durch das Verdampfen von Ammoniak kann die Reaktionswärme auf einfache Weise ohne zusätzliche Verdünnungsmittel abgeleitet werden. Aufgrund des Überschusses anMolten maleic anhydride is preferably introduced into a reactor filled with liquid ammonia. The temperature of the maleic anhydride is 60 to 100 ° C. The reaction of the maleic anhydride preferably takes place at temperatures between 60 and 100 ° C and a pressure of 26 to 64 bar. The molar ratio of maleic anhydride and ammonia is preferably at least 1: 4, it is preferably 1: 4 to 1: 500. The excess of ammonia is of particular advantage since the reaction of the anhydride with the ammonia is a very fast and highly exothermic reaction. By evaporating ammonia, the heat of reaction can be easily dissipated without additional diluents. Due to the excess
Ammoniak kann z.B. das Ammoniumsalz der Maleinamidsäure gebildet werden. Es können beispielsweise Zwischenprodukte wie Maleinsäurediammoniumsalz oder Maleinamidsäureammoniumsalz aus den oben genannten Edukten in einem getrennten Verfahrensschritt hergestellt und anschließend in Substanz oder in geeigneten Lösungsmitteln diskontinuierlich oder kontinuierlich thermisch poly- merisiert werden.For example, ammonia can form the ammonium salt of maleic acid. For example, intermediate products such as maleic acid diammonium salt or maleic acid ammonium salt can be prepared from the starting materials mentioned above in a separate process step and then thermally polymerized batchwise or continuously in bulk or in suitable solvents.
Die Erfindung betrifft deshalb auch ein Verfahren zur Herstellung von nicht polymerisierten Stickstoffverbindungen einer C,-Carbonsäure, dadurch gekennzeichnet, daß Maleinsäureanhydrid, Maleinsäure und/oder Fumarsäure mit kondensiertem flüssigem Ammoniak zu einem niedermolekularen Produkt umgesetzt werden. Dieses kann beispielsweise ein Amid, Imid oder Ammoniumsalz sein, insbesondere das Mono- oder Diammoniumsalz der Maleinsäure, Maleinamidsäure, Asparaginsäure, Iminodisuccinsäure, Iminodisuccinamidsäuren oder Asparagin.The invention therefore also relates to a process for the preparation of unpolymerized nitrogen compounds of a C, -carboxylic acid, characterized in that maleic anhydride, maleic acid and / or fumaric acid are reacted with condensed liquid ammonia to give a low molecular weight product. This can be, for example, an amide, imide or ammonium salt, in particular the mono- or diammonium salt of maleic acid, maleic acid, aspartic acid, iminodisuccinic acid, iminodisuccinamic acids or asparagine.
Die Polymerisation des Reaktionsproduktes wird im allgemeinen bei Temperaturen zwischen 100°C und 350°C, bevorzugt zwischen 120°C und 250°C, besonders bevorzugt zwischen 120°C und 220°C, durchgeführt. Die Verweilzeit beträgt vorzugsweise zwischen 1 Sekunde und 600 Minuten, bevorzugt 5 Sekunden bis 180 Minuten, besonders bevorzugt 10 Sekunden bis 150 Minuten. Sie kann beispielsweise aber auch anders, z.B. mit Mikrowellen, durchgeführt werden.The polymerization of the reaction product is generally carried out at temperatures between 100 ° C. and 350 ° C., preferably between 120 ° C. and 250 ° C., particularly preferably between 120 ° C. and 220 ° C. The residence time is preferably between 1 second and 600 minutes, preferably 5 seconds to 180 minutes, particularly preferably 10 seconds to 150 minutes. However, it can also be done differently, e.g. with microwaves.
Für die thermische Polymerisation eignen sich grundsätzlich alle Apparate, die bei einer engen Verweilzeitverteilung die notwendige Mindestverweilzeit zur Polymerisation und gleichzeitig eine zumindest partielle Verdampfung des Lösungsmittels, sowie des bei der Reaktion gebildeten Wassers ermöglichen.In principle, all apparatus are suitable for thermal polymerization which, with a narrow residence time distribution, permit the necessary minimum residence time for the polymerization and at the same time an at least partial evaporation of the solvent and of the water formed during the reaction.
Bevorzugte Vorrichtungen zur thermischen Polymerisation sind also alle Apparate, die eine definierte Verweilzeit mit einer engen Verweilzeitverteilung für die feste oder hochviskosflüssige Phase aufweisen und gleichzeitig eine gute Temperierung durch ein zumindest partielles Verdampfen des Lösungsmittels (org. Lösungsmittel und/oder Wasser) und/oder des be i der Polymeri sation gebi ldeten Reaktionswassers ermöglichen. Solche bevorzugten Vorrichtungen können beispielsweise seinPreferred devices for thermal polymerization are therefore all apparatuses which have a defined residence time with a narrow residence time distribution for the solid or highly viscous phase and at the same time good temperature control by at least partial evaporation of the solvent (organic solvent and / or water) and / or enable the water of reaction formed in the polymerization. Such preferred devices can be, for example
a) Wirbelschichtreaktoren b) Hochviskosreaktoren (z. B. Schnecke, List-Reaktor) c) Trockner (z. B. Schaufeltrockner, Sprühtrockner) Soweit es sich bei den Polymerisationsprodukten um Ringsysteme handelt, können diese durch Umsetzung mit einer Base gegebenenfalls in Gegenwart von Wasser in ein offenkettiges System, z.B. ein PAA-haltiges Copolymer-Salz überführt werden. Diese Umwandlung von z.B. PSI-haltigen in PAA-haltige Copolymere geschieht in einer geeigneten Vorrichtung durch Hydrolyse. Bevorzugt ist dabei im wässrigen System ein pH- Wert zwischen 5 und 14 geeignet. In besonders bevorzugter Form wird ein pH- Wert von 7 bis 12 gewählt, insbesondere durch den Zusatz einer Base. Geeignete Basen sind Alkali- und Erdalkalihydroxide oder Carbonate wie beispielsweise Natronlauge, Kalilauge, Soda oder Kaliumcarbonat, Ammoniak und Amine wie Triethylamin, Triethanolamin, Diethylamin, Diethanol- amin, Alkylamine etc..a) fluidized bed reactors b) high-viscosity reactors (e.g. screw, list reactor) c) dryers (e.g. paddle dryers, spray dryers) Insofar as the polymerization products are ring systems, they can be converted into an open-chain system, for example a PAA-containing copolymer salt, by reaction with a base, if appropriate in the presence of water. This conversion of, for example, PSI-containing to PAA-containing copolymers takes place in a suitable device by hydrolysis. A pH between 5 and 14 is preferably suitable in the aqueous system. In a particularly preferred form, a pH of 7 to 12 is chosen, in particular by adding a base. Suitable bases are alkali and alkaline earth metal hydroxides or carbonates such as sodium hydroxide solution, potassium hydroxide solution, sodium carbonate or potassium carbonate, ammonia and amines such as triethylamine, triethanolamine, diethylamine, diethanolamine, alkylamines etc.
Die Temperatur bei der Hydrolyse liegt vorzugsweise in einem Bereich einschließlich bis zum Siedepunkt der Succinylgruppen-haltigen Suspension oder Lösung und bevorzugt bei 20 bis 150°C. Die Hydrolyse wird gegebenenfalls unter Druck durchgeführt. Die Hydrolyse wird gegebenenfalls unter Zusatz eines weiteren monoethylenisch ungesättigten Carbonsäurederivates durchgeführt. Geeignet sind beispielsweise Maleinsäureanhydrid, Maleinsäure, Citraconsäure, Itaconsäure, Aco- nitsäure, Acrylsäure und Fumarsäure.The temperature during the hydrolysis is preferably in a range including up to the boiling point of the suspension or solution containing succinyl groups and preferably at 20 to 150 ° C. The hydrolysis is optionally carried out under pressure. The hydrolysis is optionally carried out with the addition of a further monoethylenically unsaturated carboxylic acid derivative. For example, maleic anhydride, maleic acid, citraconic acid, itaconic acid, aconitic acid, acrylic acid and fumaric acid are suitable.
Unter den basischen Bedingungen der Hydrolyse kann eine Addition der Λmino- gruppen des N-terminalen Endes des Polymermoleküls an das in der Salzform vorliegende monoethylenisch ungesättigte Carbonsäurederivat stattfinden.Under the basic conditions of hydrolysis, the amino groups of the N-terminal end of the polymer molecule can be added to the monoethylenically unsaturated carboxylic acid derivative present in the salt form.
In Abhängigkeit von den Polymerisationsbedingungen können die primären Polymerisationsprodukte auch ethylenisch ungesättigte Endgruppen besitzen. Daher kann es sinnvoll sein, dem Reaktionsgemisch während der basischen Hydrolyse gegebenenfalls auch Aminocarbonsäuren, z.B. Glycin, Asparaginsäure, Lysin,Depending on the polymerization conditions, the primary polymerization products can also have ethylenically unsaturated end groups. It may therefore be useful to optionally add aminocarboxylic acids to the reaction mixture during the basic hydrolysis, e.g. Glycine, aspartic acid, lysine,
Glutaminsäure etc., beispielsweise auch Ammoniak zuzusetzen. Durch diese Maßnahme wird eine Propfung der Polymerendgruppen erreicht.Glutamic acid etc., for example also add ammonia. A grafting of the polymer end groups is achieved by this measure.
Die Polymere zeichnen sich durch ein verbessertes Calciumbindever ögcn aus. Weiterhin zeigen sie Komplexbildungseigenschaften gegenüber Schwermetallen wie z.B. Kupfer, Eisen etc.. Sie können als Zusatz in phospatar en und phosphatfreien Wasch- und Reinigungsmitteln verwendet werden. Die Polymerisate sind Builder für Waschmittel und bewirken während des Waschvorgangs eine Verminderung der Inkrustrierung und Vergrauung auf dem gewaschenen Textilgut. Weiterhin inhibieren und verzögern die erfindungsgemäßen Polymeren die Ausfällung von Salzen, insbesondere Kristallen, z.B. von Calciumcarbonat, Calcium- sulfat, Calciumphosphat, Bariumsulfat und Magnesiumsilikat, aus wäßrigen Lösungen und sind daher als Wasserbehandlungsmittel geeignet. Sie können dem Wasser in Kühlkreisläufen, Verdampfern oder Meerwasserentsalzungsanlagen und Einpreßwässern bei der sekundären Ölforderung und Wasserbehandlung im Bergbau zugesetzt werden. Außerdem können sie als Belagsverhinderer bei der Eindampfung von Zuckersaft eingesetzt werden.The polymers are characterized by an improved calcium binding process. Furthermore, they show complexing properties compared to heavy metals such as copper, iron etc. They can be used as additives in phosphate-free and phosphate-free detergents and cleaning agents. The polymers are builders for detergents and reduce the incrustation and graying on the washed fabric during the washing process. Furthermore, the polymers according to the invention inhibit and delay the precipitation of salts, in particular crystals, for example calcium carbonate, calcium sulfate, calcium phosphate, barium sulfate and magnesium silicate, from aqueous solutions and are therefore suitable as water treatment agents. They can be added to the water in cooling circuits, evaporators or seawater desalination plants and pressurized water for secondary oil production and water treatment in mining. They can also be used as deposit inhibitors when evaporating sugar juice.
Aufgrund ihrer komplexbildenden Eigenschaft gegenüber Schwermetallen können die Copolymere auch als Stabilisierungsmittel für Bleichmittel wie Wasserstoffperoxid in Bleichprozessen dienen.Due to their complex-forming properties towards heavy metals, the copolymers can also serve as stabilizers for bleaching agents such as hydrogen peroxide in bleaching processes.
Die erfindungsgemäßen Copolymerisate sind nach den "OECD Guidelines for testing of chemicals (1981)" als biologisch abbaubar einzustufen. The copolymers according to the invention are to be classified as biodegradable according to the "OECD Guidelines for testing of chemicals (1981)".
Beispielexample
In einem 1,4 1 Autoklav mit aufgesetztem Kondensator wurden 297 g flüssiges, kondensiertes Ammoniak vorgelegt und auf eine Temperatur von 70°C erwärmt, wodurch sich ein Druck im Reaktionsgefäß von 33 bar einstellte. Anschließend wurde 90 g flüssiges Maleinsäureanhydrid bei T = 70°C in den Rührkesselreaktor gepumpt und eine Stunde gerührt. Nach einer Reaktionszeit von 1 Stunde bei 70°C wurde der Druck auf 1 bar entspannt und unter Stickstoffbegasung die Temperatur auf 170°C erhöht. Die Reaktionszeit der Polymerisation betrug 6 Stunden. Das abgekühlte Reaktionsprodukt wurde in 200 ml Wasser suspendiert und mit 40 %iger Natronlauge bis zu einem pH- Wert von 8,5 gelöst. Die297 g of liquid, condensed ammonia were placed in a 1.4 liter autoclave with a condenser attached and heated to a temperature of 70 ° C., which resulted in a pressure in the reaction vessel of 33 bar. 90 g of liquid maleic anhydride were then pumped into the stirred tank reactor at T = 70 ° C. and the mixture was stirred for one hour. After a reaction time of 1 hour at 70 ° C., the pressure was released to 1 bar and the temperature was raised to 170 ° C. while gassing with nitrogen. The reaction time of the polymerization was 6 hours. The cooled reaction product was suspended in 200 ml of water and dissolved with 40% sodium hydroxide solution to a pH of 8.5. The
Ausbeute des Natriumsalzes der Polyasparaginsäure betrug 123 g. Das mittels Gelpermeationschromatographie bestimmte Gewichtsmittel der Molmassen lag bei ca. 1750 g/mol, der ß-Anteil bei ca. 70 %. Yield of the sodium salt of polyaspartic acid was 123 g. The weight average molecular weight determined by means of gel permeation chromatography was approx. 1750 g / mol, the ß fraction approx. 70%.

Claims

Patentansprüche claims
1. Verfahren zur Herstellung von Polymeren mit wiederkehrenden Succinyleinheiten, dadurch gekennzeichnet, daß Maleinsäureanhydrid, Maleinsäure und/oder Fumarsäure, gegebenenfalls in Gegenwart von Comonomeren mit kondensiertem flüssigem Ammoniak umgesetzt werden und das erhaltene1. A process for the preparation of polymers with recurring succinyl units, characterized in that maleic anhydride, maleic acid and / or fumaric acid, optionally in the presence of comonomers, are reacted with condensed liquid ammonia and the resultant
Reaktionsprodukt polymerisiert und gegebenenfalls hydrolysiert wird.The reaction product is polymerized and optionally hydrolyzed.
2. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß Maleinsäureanhydrid mit kondensiertem flüssigem Ammoniak umgesetzt wird.2. The method according to claim 1, characterized in that maleic anhydride is reacted with condensed liquid ammonia.
3. Verfahren nach wenigstens einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, daß pro Mol Maleinsäureanhydrid, Maleinsäure oder3. The method according to at least one of the preceding claims, characterized in that per mole of maleic anhydride, maleic acid or
Fumarsäure wenigstens 4 Mol Ammoniak eingesetzt werden.Fumaric acid at least 4 moles of ammonia can be used.
4. Verfahren nach wenigstens einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, daß die Umsetzung in flüssigem Ammoniak bei 60 bis 100°C und einem Druck von 26 bis 64 bar durchgeführt werden.4. The method according to at least one of the preceding claims, characterized in that the reaction in liquid ammonia at 60 to 100 ° C and a pressure of 26 to 64 bar are carried out.
5. Verfahren nach wenigstens einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, daß die Polymerisation bei 100 bis 350°C, insbesondere bei 120 bis 220°C durchgeführt wird.5. The method according to at least one of the preceding claims, characterized in that the polymerization is carried out at 100 to 350 ° C, in particular at 120 to 220 ° C.
6. Verfahren nach wenigstens einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, daß die Polymerisation unter Verwendung von Mikro- wellen erreicht wird.6. The method according to at least one of the preceding claims, characterized in that the polymerization is achieved using microwaves.
7. Verfahren nach wenigstens einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, daß die bei der Umsetzung im flüssigen Ammoniak entstehende Reaktionswärme durch Siedekühlung mittels Ammoniak abgeführt wird.7. The method according to at least one of the preceding claims, characterized in that the heat of reaction arising in the reaction in liquid ammonia is removed by evaporative cooling using ammonia.
8. Verfahren nach wenigstens einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, daß der durch die Siedekühlung verdampfte Ammoniak und der bei der Polymerisation freiwerdende Ammoniak zurückgeführt wird. 8. The method according to at least one of the preceding claims, characterized in that the ammonia evaporated by the evaporative cooling and the ammonia released during the polymerization are returned.
9. Verfahren nach wenigstens einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, daß das erhaltene Polymer nach Hydrolyse ein Molekulargewicht von 500 bis 6000 Mw aufweist.9. The method according to at least one of the preceding claims, characterized in that the polymer obtained has a molecular weight of 500 to 6000 Mw after hydrolysis.
10. Verfahren nach wenigstens einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, daß das nach Hydrolyse erhaltene Produkt mit einer Base hydrolysiert wird.10. The method according to at least one of the preceding claims, characterized in that the product obtained after hydrolysis is hydrolyzed with a base.
1 1. Verfahren zur Herstellung von niedermolekularen Stickstoffverbindungen einer C4-Dicarbonsäure, dadurch gekennzeichnet, daß man Maleinsäure, Maleinsäureanhydrid oder Fumarsäure mit kondensiertem flüssigem Ammoniak umsetzt.1 1. Process for the preparation of low molecular weight nitrogen compounds of a C 4 dicarboxylic acid, characterized in that maleic acid, maleic anhydride or fumaric acid is reacted with condensed liquid ammonia.
12. Verfahren gemäß Anspruch 11 , dadurch gekennzeichnet, daß man das erhaltene Reaktionsprodukt abtrennt. 12. The method according to claim 11, characterized in that separating the reaction product obtained.
EP97940126A 1996-09-06 1997-08-25 Process for preparing polymers with recurring succinyl units Withdrawn EP0927216A1 (en)

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US6365706B1 (en) * 2000-06-21 2002-04-02 Mississippi Chemical Corporation Process for production of polyasparagine and the high nitrogen content polymer formed thereby
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KR101411041B1 (en) * 2010-02-18 2014-06-27 미쓰이 가가쿠 가부시키가이샤 Processes for production of polyaspartic acid precursor polymer and polyaspartic acid salts
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US5288783A (en) * 1992-05-14 1994-02-22 Srchem Incorporated Preparation of salt of polyaspartic acid by high temperature reaction
US5393868A (en) * 1992-10-13 1995-02-28 Rohm And Haas Company Production of polysuccinimide by thermal polymerization of maleamic acid
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