EP0000361A1 - Process for the preparation of poly(phenylene-oxy-phenylene-sulfone) - Google Patents
Process for the preparation of poly(phenylene-oxy-phenylene-sulfone) Download PDFInfo
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- EP0000361A1 EP0000361A1 EP78100283A EP78100283A EP0000361A1 EP 0000361 A1 EP0000361 A1 EP 0000361A1 EP 78100283 A EP78100283 A EP 78100283A EP 78100283 A EP78100283 A EP 78100283A EP 0000361 A1 EP0000361 A1 EP 0000361A1
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- sulfone
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- dichlorobenzene
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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
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/34—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives
- C08G65/38—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives derived from phenols
- C08G65/40—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives derived from phenols from phenols (I) and other compounds (II), e.g. OH-Ar-OH + X-Ar-X, where X is halogen atom, i.e. leaving group
- C08G65/4093—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives derived from phenols from phenols (I) and other compounds (II), e.g. OH-Ar-OH + X-Ar-X, where X is halogen atom, i.e. leaving group characterised by the process or apparatus used
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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
- C08G75/00—Macromolecular compounds obtained by reactions forming a linkage containing sulfur with or without nitrogen, oxygen, or carbon in the main chain of the macromolecule
- C08G75/20—Polysulfones
- C08G75/23—Polyethersulfones
Definitions
- the invention relates to a process for the production of polyethers, in particular polyethers containing sulfone groups.
- polysulfone ethers are preferably prepared by reacting aromatic alkali phenolates with aromatic halogen compounds. Aqueous solutions of the alkali metal hydroxide are added in the preparation of the alkali metal salt. Exactly stoichiometric amounts must be adhered to here, since an excess or deficit of the base leads to unsatisfactory molecular weights. In addition, large phenolate agglomerates often form due to the water present, which can lead to considerable disturbances in the polycondensation.
- Suitable bisphenols are compounds which differ from the general formula can be derived in which Ar is an aromatic radical with 6 carbon atoms, A is a divalent radical from the group -S0 2 -, -CO- and n and m is 0 or 1.
- Such bisphenols are, for example, hydroquinone, resorcinol, 4,4f-bisphenol, bis (4-oxyphenyl) sulfone and bis (4-oxyphenyl) ketone.
- the bisphenols mentioned can be used individually or in the form of mixtures.
- Bis (4-oxyphenyl) sulfone is preferably used.
- Derivatives of the general formulas are suitable as dichlorobenzene compounds in which B represents the radical -CO- or -S0 2 -, D represents -0-or -S- and x is 0 or 1.
- dichlorobenzene compounds examples include: bis (4-chlorophenyl) sulfone, bis (4-chlorophenyl) ketone, 1,4-bis (4-chlorobenzoyl) benzene, 1,4-bis (4- chlorobenzenesulfonyl) benzene, 4,4'-bis (4-chlorobenzoyl) diphenyl ether, 4,4'-bis (4-chlorobenzyl) diphenyl sulfide, 4,4'-bis (4-chlorobenzoyl) diphenyl, 4,4'-bis (4-chlorobenzenesulfonyl) diphenyl ether, 4,4'-bis (4-chlorobenzenesulfonyl) diphenyl sulfide or 4,4'-bis (4-chlorobenzenesulfonyl) diphenyl.
- the dichlorobenzene compounds can also be used individually or as a mixture.
- N-substituted acid amides the sulfoxides or sulfones
- N-substituted acid amides for example N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone, dimethyl sulfoxide, dimethyl sulfone, tetramethylene sulfone (sulfolane) or, are used as polar, aprotic solvents Diphenyl sulfone.
- N-methylpyrrolidone is preferably used.
- the polar, aprotic solvents are used in amounts of 5 to 100, preferably 10 to 20, moles, based on one mole of bisphenol or dichlorobenzene compound. This means that the reaction solutions in the absence of alkali carbonate and azeotroping agent have a solids content of 5 to 50% by weight, preferably 20 to 35% by weight, based on the total weight.
- anhydrous alkali carbonates are sodium and preferably potassium carbonate.
- 1 to 2 preferably 1.0 to 1.2, mol of anhydrous alkali metal carbonate are used per mole of bisphenol and dichlorobenzene compound.
- Suitable water azeotroping agents are all substances which boil in the range of the reaction temperature at normal pressure can be mixed homogeneously with the reaction mixture without undergoing chemical reactions.
- azeotroping agents of the type mentioned are: chlorobenzene, toluene and xylene.
- Chlorobenzene is preferred.
- the azeotroping agents are used in amounts such that the quantitative separation of the water formed during the neutralization of hydrogen chloride and alkali carbonate is ensured.
- the amount of azeotroping agent required also depends on the type and size of the device. However, the required amount can easily be determined experimentally.
- azeotrope is not circulated, it has proven to be advantageous to use about 2 to 10 moles of azeotrope per mole of alkali metal carbonate in the first reaction stage.
- the process according to the invention is preferably used for the polycondensation of about 1 mol of bis (4-oxyphenyl) sulfone with about 1 mol of bis (4-chlorophenyl) sulfone in N-methylpyrrolidone as an aprotic solvent in the presence of 1.0 to 1.2 Mol of anhydrous potassium carbonate and chlorobenzene used as water azeotrope to polyethers.
- the reaction mixture in the first reaction stage is separated off at least 90% by weight, preferably 90 to 96% by weight, based on the total weight, of what is theoretically possible amount of water advantageously heated for 0.5 to 4 hours, preferably 1 to 2 hours.
- the reaction mixture is polycondensed until completely water-free and for this purpose, the reaction mixture is continuously mixed with further azeotrope and the azeotrope mixture formed is distilled off simultaneously.
- the reaction time is approximately 1.5 to 4 hours, preferably 1 to 2 hours.
- the polycondensation is then stopped by introducing methyl chloride.
- the reaction time for this is approximately 0.1 to 2, preferably 0.2 to 0.5 hours.
- the isolation of the polyether in the fourth stage can be carried out in various ways.
- the solid polymer can be separated by mixing the reaction solution with a precipitant, e.g. Water and / or methanol, by vigorous stirring, splashing or atomizing.
- a precipitant e.g. Water and / or methanol
- the solvent can also be evaporated.
- the inorganic constituents can be removed from the polyether by suitable methods such as dissolving, filtering or sieving.
- the polyethers produced using the process according to the invention have reduced viscosities (measured at 24 ° C. in a 1% strength sulfuric acid solution) from 0.4 to 1.5. This corresponds to molecular weights of 15,000 to 120,000.
- the polyethers produced are particularly suitable for the production of moldings, fibers, films, adhesives and coating materials.
- the invention is illustrated by the following examples and comparative examples.
- the parts mentioned are parts by weight.
- the reduced viscosities ( ⁇ red ) were measured at 24 ° C in 1% sulfuric acid solution and according to the formula certainly.
- the color evaluation of the polyethers was carried out by UV measurement on 1% sulfuric acid solutions.
- the light transmittance of the solution was measured in the range from 400 to 800 m ⁇ at intervals of 50 m / u and the average transmittance was calculated from this.
- Example 3 Analogously to Example 3, 66.1 parts of resorcinol are used for the reaction.
Abstract
Polyäther, vorzugsweise sulfongruppenhaltige Polyäther, werden in einem mehrstufigen Kondensationsverfahren bei Temperaturen von 100 bis 230° C aus im wesentlichen äquivalenten Mengen eines Bisphenols und einer Dichlorbenzolverbindung in einem polaren, aprotischen Lösungsmittel in Gegenwart von wasserfreiem Alkalicarbonat und gegebenenfalls eines Azeotropbildners hergestellt. Die nach dem erfindungsgemässen Verfahren hergestellten Polyäther besitzen Molekulargewichte von 15 000 bis 120 000 und eignen sich vorzüglich zur Herstellung von Formkörpern, Fasern, Folien, Kleb- und Beschichtungsstoffen.Polyethers, preferably sulfone-containing polyethers, are produced in a multi-stage condensation process at temperatures from 100 to 230 ° C. from essentially equivalent amounts of a bisphenol and a dichlorobenzene compound in a polar, aprotic solvent in the presence of anhydrous alkali carbonate and optionally an azeotroping agent. The polyethers produced by the process according to the invention have molecular weights of 15,000 to 120,000 and are particularly suitable for the production of moldings, fibers, films, adhesives and coating materials.
Description
Die Erfindung betrifft ein Verfahren zur Herstellung von Polyäthern, insbesondere sulfongruppenhaltigen Polyäthern.The invention relates to a process for the production of polyethers, in particular polyethers containing sulfone groups.
Polymere mit Sulfon- und Äthergruppen sind bereits bekannt. Nach Angaben der DT-OS 15 45 106 und DT-OS 17 95 725 werden Polysulfonäther vorzugsweise durch Umsetzung aromatischer Alkaliphenolate mit aromatischen Halogenverbindungen hergestellt. Bei der Herstellung des Alkalisalzes werden wäßrige Lösungen des Alkalihydroxids zugegeben. Hierbei müssen exakt stöchiometrische Mengen eingehalten werden, da ein Über- oder Unterschuß der Base zu unbefriedigenden Molekulargewichten führt. Außerdem bilden sich aufgrund des anwesenden Wassers häufig große Phenolatagglomerate, die zu erheblichen Störungen bei der Polykondensation führen können.Polymers with sulfone and ether groups are already known. According to DT-OS 15 45 106 and DT-OS 17 95 725, polysulfone ethers are preferably prepared by reacting aromatic alkali phenolates with aromatic halogen compounds. Aqueous solutions of the alkali metal hydroxide are added in the preparation of the alkali metal salt. Exactly stoichiometric amounts must be adhered to here, since an excess or deficit of the base leads to unsatisfactory molecular weights. In addition, large phenolate agglomerates often form due to the water present, which can lead to considerable disturbances in the polycondensation.
In der DT-OS 19 57 091 sowie in der CA-PS 847 963 werden die beschriebenen Nachteile teilweise durch Verwendung von wasserfreiem Alkalicarbonat beseitigt. Nach Angaben der DT-OS 19 57 091 werden jedoch die geringen Wassermengen, die sich beim Zerfall des in situ entstehenden Alkalibicarbonates bilden, nicht entfernt. Dadurch ergeben sich ungenügende Molekulargewichte, und das Verfahren ist nur mit wenigen ausgewählten Monomeren durchführbar. In der CA-PS 847 963 wird dieser Nachteil durch Verwendung eines Lösungsmittels vermieden, das azeotrop mit Wasser abdestilliert. Zum Erreichen befriedigender Molekulargewichte werden hier allerdings relativ hohe Temperaturbereiche eingestellt, die zu mehr oder minder verfärbten Produkten führen. Außerdem ist das Verfahren auf wenige, hochsiedende Lösungsmittel beschränkt.In DT-OS 19 57 091 and in CA-PS 847 963 the disadvantages described are partially eliminated by using anhydrous alkali carbonate. According to DT-OS 19 57 091, however, the small amounts of water which form when the alkali metal bicarbonate formed in situ decay are not removed. This results in insufficient molecular weights and the process can only be carried out with a few selected monomers. In CA-PS 847 963 this disadvantage is avoided by using a solvent the one that distills off azeotropically with water. To achieve satisfactory molecular weights, however, relatively high temperature ranges are set here, which lead to more or less discolored products. In addition, the process is limited to a few high-boiling solvents.
Überraschenderweise wurde nun gefunden, daß man bei niedrigeren Reaktionstemperaturen Polyäther mit guter Eigenfarbe und hohem Molekulargewicht erhält, wenn man im wesentlichen äquivalente Mengen eines Bisphenols mit einer Dichlorbenzolverbindung in einem polar aprotischen Lösungsmittel in Gegenwart von wasserfreiem Alkalicarbonat stufenweise umsetzt.Surprisingly, it has now been found that polyethers with a good inherent color and high molecular weight are obtained at lower reaction temperatures if essentially equivalent amounts of a bisphenol are reacted stepwise with a dichlorobenzene compound in a polar aprotic solvent in the presence of anhydrous alkali metal carbonate.
Gegenstand der Erfindung ist daher ein Verfahren zur Herstellung von Polyäthern durch Umsetzung von im wesentlichen äquivalenten Mengen eines Bisphenols oder einer Mischung mehrerer Bisphenole mit einer Dichlorbenzolverbindung oder einer Mischung mehrerer Dichlorbenzolverbindungen in einem polaren, aprotischen Lösungsmittel in Gegenwart von wasserfreiem Alkalicarbonat, das dadurch gekennzeichnet ist, daß
- a) in einer ersten Reaktionsstufe eine Lösung von einem Mol Bisphenol mit ungefähr einem Mol der Dichlorbenzolverbindung in Gegenwart von 1 bis 2, vorzugsweise 1,0 bis 1,2 Mol wasserfreiem Alkalicarbonat und eines Wasser-Azeotropbildners bis zur Abtrennung von mindestens 90 Gew.%, bezogen auf das Gesamtgewicht, der theoretisch möglichen Wassermenge bei Temperaturen von 100°C bis 1700C. vorzugsweise 120°C bis 150°C umgesetzt wird,
- b) in einer zweiten Reaktionsstufe das Reaktionsgemisch bei Temperaturen von 150°C bis 230oC, vorzugsweise 170°C bis 200°C mit weiterem Azeotropbildner versetzt und gleichzeitig das entstehende azeotrope Gemisch bis zur völligen Wasserfreiheit abdestilliert wird,
- c) in einer dritten Reaktionsstufe das Reaktionsgemisch bei Temperaturen von 150°C bis 230oC, vorzugsweise 170°C bis 200°C bis zu einer reduzierten Viskosität von 0,4 bis 1,5 polykondensiert und anschließend die Polymerisation durch Zugabe von Methylchlorid abgestoppt wird und
- d) der entstandene Polyäther durch an sich bekannte Maßnahmen von Lösungsmitteln und anorganischen Bestandteilen abgetrennt wird.
- a) in a first reaction stage, a solution of one mole of bisphenol with about one mole of the dichlorobenzene compound in the presence of 1 to 2, preferably 1.0 to 1.2 moles of anhydrous alkali carbonate and a water azeotrope to remove at least 90% by weight , based on the total weight of the theoretically possible amount of water at temperatures of 100 ° C to 170 0 C., preferably 120 ° C to 150 ° C is reacted
- b) in a second reaction step, the reaction mixture at temperatures of 150 ° C to 230 o C, preferably 170 ° C to 200 ° C with additional azeotrope was added and simultaneously the resulting azeotropic mixture is distilled off until the complete absence of water,
- c polycondensed) in a third reaction step the reaction mixture at temperatures of 150 ° C to 230 o C, preferably 170 ° C to 200 ° C up to a reduced viscosity of 0.4 to 1.5, and then stopped, the polymerization by the addition of methylene chloride will and
- d) the polyether formed is separated from solvents and inorganic constituents by measures known per se.
Als Bisphenole eignen sich Verbindungen, die sich von der allgemeinen Formel
Derartige Bisphenole sind beispielsweise Hydrochinon, Resorcin, 4,4f-Bisphenol, Bis-(4-oxyphenyl-)sulfon und Bis-(4-oxy- phenyl-)-keton. Die genannten Bisphenole können einzeln oder in Form von Mischungen zur Anwendung kommen. Vorzugsweise verwendet wird Bis-(4-oxyphenyl-)sulfon.Such bisphenols are, for example, hydroquinone, resorcinol, 4,4f-bisphenol, bis (4-oxyphenyl) sulfone and bis (4-oxyphenyl) ketone. The bisphenols mentioned can be used individually or in the form of mixtures. Bis (4-oxyphenyl) sulfone is preferably used.
Als Dichlorbenzolverbindungen eignen sich Derivate der allgemeinen Formeln
Als derartige Dichlorbenzolverbindungen seien beispielsweise genannt: Bis-(4-chlorphenyl-)sulfon, Bis-(4-chlorphenyl-) keton, 1,4-Bis-(4-chlorbenzoyl-)benzol, 1,4-Bis-(4-chlor- benzolsulfonyl-)benzol, 4,4'-Bis-(4-chlorbenzoyl-)diphenyläther, 4,4'-Bis-(4-chlorbenzyl-)diphenylsulfid, 4,4'-Bis-(4-chlorbenzoyl-)diphenyl, 4,4'-Bis-(4-chlorbenzolsulfonyl-) diphenyläther, 4,4'-Bis-(4-chlorbenzolsulfonyl-)diphenyl- sulfid oder 4,4'-Bis-(4-chlorbenzolsulfonyl-)diphenyl. Die Dichlorbenzolverbindungen können ebenfalls einzeln oder als Gemisch verwendet werden. Vorzugsweise verwendet wird Bis-(4-chlorphenyl)-sulfon.Examples of such dichlorobenzene compounds are: bis (4-chlorophenyl) sulfone, bis (4-chlorophenyl) ketone, 1,4-bis (4-chlorobenzoyl) benzene, 1,4-bis (4- chlorobenzenesulfonyl) benzene, 4,4'-bis (4-chlorobenzoyl) diphenyl ether, 4,4'-bis (4-chlorobenzyl) diphenyl sulfide, 4,4'-bis (4-chlorobenzoyl) diphenyl, 4,4'-bis (4-chlorobenzenesulfonyl) diphenyl ether, 4,4'-bis (4-chlorobenzenesulfonyl) diphenyl sulfide or 4,4'-bis (4-chlorobenzenesulfonyl) diphenyl. The dichlorobenzene compounds can also be used individually or as a mixture. Bis (4-chlorophenyl) sulfone is preferably used.
Als polare, aprotische Lösungsmittel gelangen Verbindungen zur Anwendung, die zu den N-substituierten Säureamiden, den Sulfoxiden oder Sulfonen zählen, beispielsweise N,N-Dimethylformamid, N,N-Dimethylacetamid, N-Methylpyrrolidon, Dimethylsulfoxid, Dimethylsulfon, Tetramethylensulfon (Sulfolan) oder Diphenylsulfon. Bevorzugt wird N-Methylpyrrolidon verwendet.Compounds which belong to the N-substituted acid amides, the sulfoxides or sulfones, for example N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone, dimethyl sulfoxide, dimethyl sulfone, tetramethylene sulfone (sulfolane) or, are used as polar, aprotic solvents Diphenyl sulfone. N-methylpyrrolidone is preferably used.
Die polaren, aprotischen Lösungsmittel werden in'Mengen von 5 bis 100, vorzugsweise von 10 bis 20 Molen, bezogen auf ein Mol Bisphenol oder Dichlorbenzolverbindung, verwendet. Dies bedeutet, daß die Reaktionslösungen in Abwesenheit von Alkalicarbonat und Azeotropbildner einen Feststoffgehalt von 5 bis 50 Gew.%, vorzugsweise von 20 bis 35 Gew.%, bezogen auf das Gesamtgewicht, aufweisen.The polar, aprotic solvents are used in amounts of 5 to 100, preferably 10 to 20, moles, based on one mole of bisphenol or dichlorobenzene compound. This means that the reaction solutions in the absence of alkali carbonate and azeotroping agent have a solids content of 5 to 50% by weight, preferably 20 to 35% by weight, based on the total weight.
Als wasserfreie Alkalicarbonate kommen beispielsweise Natrium- und vorzugsweise Kaliumcarbonat in Betracht. Zur Neutralisation des bei der Polykondensation entstehenden Chlorwas- .serstoffs werden pro Mol Bisphenol und Dichlorbenzolverbindung 1 bis 2, vorzugsweise 1,0 bis 1,2 Mol wasserfreies Alkalicarbonat eingesetzt.Examples of suitable anhydrous alkali carbonates are sodium and preferably potassium carbonate. To neutralize the hydrogen chloride formed in the polycondensation, 1 to 2, preferably 1.0 to 1.2, mol of anhydrous alkali metal carbonate are used per mole of bisphenol and dichlorobenzene compound.
Geeignete Wasser-Azeotropbildner sind alle Substanzen, die im Bereich der Reaktionstemperatur bei Normaldruck sieden und sich mit dem Reaktionsgemisch homogen mischen lassen, ohne chemische Reaktionen einzugehen. Als Azeotropbildner der genannten Art seien beispielsweise genannt: Chlorbenzol, Toluol und Xylol.Suitable water azeotroping agents are all substances which boil in the range of the reaction temperature at normal pressure can be mixed homogeneously with the reaction mixture without undergoing chemical reactions. Examples of azeotroping agents of the type mentioned are: chlorobenzene, toluene and xylene.
Bevorzugt zur Anwendung gelangt Chlorbenzol.Chlorobenzene is preferred.
Die Azeotropbildner werden in solchen Mengen verwendet, daß die quantitative Abtrennung des bei der Neutralisation von Chlorwasserstoff und Alkalicarbonat entstehenden Wassers gewährleistet wird.The azeotroping agents are used in amounts such that the quantitative separation of the water formed during the neutralization of hydrogen chloride and alkali carbonate is ensured.
Da die Wasserabtrennung in üblichen Vorrichtungen, beispielsweise Wasserabscheidern verschiedener Art, durchgeführt werden kann, wobei der Azeotropbildner gegebenenfalls ständig im Kreislauf geführt werden kann, ist die benötigte Azeotropbildnermenge auch von der Art und Größe der Vorrichtung abhängig. Die erforderliche Menge kann jedoch auf einfache Weise experimentell bestimmt werden.Since the water can be separated off in conventional devices, for example water separators of various types, the azeotroping agent possibly being continuously circulated, the amount of azeotroping agent required also depends on the type and size of the device. However, the required amount can easily be determined experimentally.
Sofern der Azeotropbildner nicht im Kreislauf geführt wird, hat es sich als zweckmäßig erwiesen, pro Mol Alkalicarbonat in der ersten Reaktionsstufe ungefähr 2 bis 10 Mol Azeotropbildner zu verwenden.If the azeotrope is not circulated, it has proven to be advantageous to use about 2 to 10 moles of azeotrope per mole of alkali metal carbonate in the first reaction stage.
Das erfindungsgemäße Verfahren wird vorzugsweise zur Polykondensation von etwa 1 Mol Bis-(4-oxyphenyl-)sulfon mit etwa 1 Mol Bis-(4-chlorphenyl-)sulfon in N-Methylpyrrolidon als aprotischem Lösungsmittel in Gegenwart von 1,0 bis 1,2 Mol wasserfreiem Kaliumcarbonat und Chlorbezol als Wasser-Azeotropbildner zu Polyäthern verwendet.The process according to the invention is preferably used for the polycondensation of about 1 mol of bis (4-oxyphenyl) sulfone with about 1 mol of bis (4-chlorophenyl) sulfone in N-methylpyrrolidone as an aprotic solvent in the presence of 1.0 to 1.2 Mol of anhydrous potassium carbonate and chlorobenzene used as water azeotrope to polyethers.
Zur Durchführung des erfindungsgemäßen Verfahrens wird die Reaktionsmischung in der ersten Reaktionsstufe bis zur Abtrennung von mindestens 90 Gew.%, vorzugsweise 90 bis 96 Gew.%, bezogen auf das Gesamtgewicht, der theoretisch möglichen Wassermenge vorteilhafterweise 0,5 bis 4 Stunden, vorzugsweise 1 bis 2 Stunden, erhitzt.To carry out the process according to the invention, the reaction mixture in the first reaction stage is separated off at least 90% by weight, preferably 90 to 96% by weight, based on the total weight, of what is theoretically possible amount of water advantageously heated for 0.5 to 4 hours, preferably 1 to 2 hours.
In der zweiten Reaktionsstufe wird das Reaktionsgemisch bis zur völligen Wasserfreiheit polykondensiert und hierzu wird das Reaktionsgemisch ständig mit weiterem Azeotropbildner versetzt und gleichzeitig das entstehende Azeotropgemisch abdestilliert. Die Reaktionszeit beträgt ungefähr b,5 bis 4 Stunden, vorzugsweise 1 bis 2 Stunden.In the second reaction stage, the reaction mixture is polycondensed until completely water-free and for this purpose, the reaction mixture is continuously mixed with further azeotrope and the azeotrope mixture formed is distilled off simultaneously. The reaction time is approximately 1.5 to 4 hours, preferably 1 to 2 hours.
Die Reaktionszeit in der dritten Stufe zur Polykondensation bis zu einer reduzierten Viskosität von 0,4 bis 1,5, vorzugs. weise 0,50 bis 1,2, des Polyäthers beträgt ungefähr 3 bis 12 Stunden, vorzugsweise 4 bis 8 Stunden. Danach wird die Polykondensation durch Einleiten von Methylchlorid abgestoppt. Die Reaktionszeit hierfür beträgt ungefähr 0,1 bis 2, vorzugsweise 0,2 bis 0,5 Stunden.The reaction time in the third stage for polycondensation to a reduced viscosity of 0.4 to 1.5, preferably. example, 0.50 to 1.2, the polyether is about 3 to 12 hours, preferably 4 to 8 hours. The polycondensation is then stopped by introducing methyl chloride. The reaction time for this is approximately 0.1 to 2, preferably 0.2 to 0.5 hours.
Die Isolierung des Polyäthers in der vierten Stufe schließlich kann auf verschiedene Weise durchgeführt werden. Eine Abscheidung des festen Polymeren kann durch Mischung der Reaktionslösung mit einem Fällungsmittel, z.B. Wasser und/oder Methanol, durch starkes Rühren, Verspritzen oder Verdüsen geschehen. Andererseits kann das Lösungsmittel auch verdampft werden. Die anorganischen Bestandteile können durch geeignete Methoden wie Lösen, Filtrieren oder Sieben aus dem Polyäther entfernt werden.Finally, the isolation of the polyether in the fourth stage can be carried out in various ways. The solid polymer can be separated by mixing the reaction solution with a precipitant, e.g. Water and / or methanol, by vigorous stirring, splashing or atomizing. On the other hand, the solvent can also be evaporated. The inorganic constituents can be removed from the polyether by suitable methods such as dissolving, filtering or sieving.
Die mit Hilfe des erfindungsgemäßen Verfahrens hergestellten Polyäther besitzen reduzierte Viskositäten (gemessen bei 24°C in 1 %iger Schwefelsäurelösung) von 0,4 bis 1,5. Dies entspricht Molekulargewichten von 15 000 bis 120 000. Die hergestellten Polyäther sind vorzüglich zur Herstellung von Formkörpern, Fasern, Folien, Kleb- und Beschichtungsstoffen geeignet.The polyethers produced using the process according to the invention have reduced viscosities (measured at 24 ° C. in a 1% strength sulfuric acid solution) from 0.4 to 1.5. This corresponds to molecular weights of 15,000 to 120,000. The polyethers produced are particularly suitable for the production of moldings, fibers, films, adhesives and coating materials.
Die Erfindung wird durch die nachfolgenden Beispiele und Vergleichsbeispiele näher erläutert. Die genannten Teile sind Gewichtsteile. Die reduzierten Viskositäten (η red) wurden bei 24°C in 1 %lger Schwefelsäurelösung gemessen und entsprechend der Formel
Die Farbbeurteilung der Polyäther wurde durch UV-Messung an 1 %igen Schwefelsäurelösungen durchgeführt. Dazu wurde die Lichtdurchlässigkeit der Lösung im Bereich von 400 bis 800 mµ in Intervallen von 50 m/u gemessen und daraus die durchschnittliche Durchlässigkeit berechnet.The color evaluation of the polyethers was carried out by UV measurement on 1% sulfuric acid solutions. For this purpose, the light transmittance of the solution was measured in the range from 400 to 800 mµ at intervals of 50 m / u and the average transmittance was calculated from this.
150,2 Teile Bis-(4-oxyphenyl-)sulfon und 172,3 Teile Bis-(4- chlorphenyl-)sulfon werden. in 900 Teilen N-Methylpyrrolidon und 300 Teilen Chlorbenzol gelöst und mit 87,2 Teilen wasserfreiem Kaliumcarbonat versetzt. Das Reaktionsgemisch wird unter ständigem Abdestillieren eines Gemisches aus Wasser und Chlorbenzol innerhalb von zwei Stunden auf 150°C erhitzt. Anschließend wird die Temperatur auf 180°C gesteigert. Innerhalb weiterer zwei Stunden werden nochmals 300 Teile Chlorbenzol zugetropft, die sofort wieder azeotrop abdestillieren. Das Reaktionsgemisch wird dann 6 Stunden bei 180°C bis zu einer reduzierten Viskosität von 0,6 gehalten. Durch 30-minütiges Einleiten eines Methylchlorid-Stromes wird die Polykondensation abgebrochen. Die anorganischen Bestandteile werden nach Zugabe von 600 ml Chlorbenzol abfiltriert, das Polymere in Wasser ausgefällt und 12 Stunden bei 80°C im Vakuum getrocknet. Es besitzt eine reduzierte Viskosität von ηred = 0,60 und eine durchschnittliche Lichtdurchlässigkeit von 3,4 %.150.2 parts of bis (4-oxyphenyl) sulfone and 172.3 parts of bis (4-chlorophenyl) sulfone. dissolved in 900 parts of N-methylpyrrolidone and 300 parts of chlorobenzene and mixed with 87.2 parts of anhydrous potassium carbonate. The reaction mixture is heated to 150.degree. C. over the course of two hours, while continuously distilling off a mixture of water and chlorobenzene. The temperature is then increased to 180 ° C. Another 300 parts of chlorobenzene are added dropwise within a further two hours, which immediately distill off again azeotropically. The reaction mixture is then kept at 180 ° C. for 6 hours to a reduced viscosity of 0.6. The polycondensation is terminated by introducing a stream of methyl chloride for 30 minutes. After the addition of 600 ml of chlorobenzene, the inorganic constituents are filtered off, the polymer is precipitated in water and dried in vacuo at 80 ° C. for 12 hours. It has a reduced viscosity of η red = 0.60 and an average light transmission of 3.4%.
Verfährt man analog den Angaben von Beispiel 1, verwendet jedoch anstelle des Kaliumcarbonats 66,8 Teile wasserfreies Natriumcarbonat, so erhält man einen Polyäther mit einer reduzierten Viskosität von ηred = 0,45 und einer durchschnittlichen Lichtdurchlässigkeit von 3,7 %.If the procedure is analogous to that of Example 1, but 66.8 parts of anhydrous sodium carbonate are used instead of the potassium carbonate, a polyether with a reduced viscosity of η red = 0.45 and an average light transmittance of 3.7% is obtained.
Die Polykondensation wird analog Beispiel 1, jedoch in Abwesenheit des Chlorbenzols durchgeführt. Man erhält einen Polyäther der reduzierten Viskosität ηred = 0,25 mit einer durchschnittlichen Absorption von 6,1The polycondensation is carried out analogously to Example 1, but in the absence of chlorobenzene. A polyether of reduced viscosity η red = 0.25 with an average absorption of 6.1 is obtained
Die Polykondensation wird entsprechend Beispiel 1, jedoch unter Verwendung von 900 Teilen Tetramethylensulfon (Sulfolan) anstelle des N-Methylpyrrolidons als Lösungsmittel durchgeführt. Ferner wird das Reaktionsgemisch in der dritten Reaktionsstufe 6 Stunden bei 235°C polykondensiert. Das erhaltene Polymere besitzt eine reduzierte Viskosität von ηred = 0,50 und eine durchschnittliche Absorption von 14,5 %.The polycondensation is carried out in accordance with Example 1, but using 900 parts of tetramethylene sulfone (sulfolane) instead of the N-methylpyrrolidone as solvent. Furthermore, the reaction mixture is polycondensed in the third reaction stage at 235 ° C. for 6 hours. The polymer obtained has a reduced viscosity of η red = 0.50 and an average absorption of 14.5%.
Man verfährt analog den Angaben des Beispiels 1, setzt jedoch das gesamte Chlorbenzol (600 Teile) dem Reaktionsgemisch bereits zu Beginn der Polykondensation hinzu und führt die Reaktion bei 180°C unter azeotroper Destillation zu Ende. Man erhält ein Oligomeres mit einer reduzierten Viskosität von ηred = 0,10 und einer durchschnittlichen Absorption von 5,8 %.The procedure is analogous to that of Example 1, but all the chlorobenzene (600 parts) is added to the reaction mixture at the beginning of the polycondensation and the reaction is ended at 180 ° C. with azeotropic distillation. An oligomer with a reduced viscosity of η red = 0.10 and an average absorption of 5.8% is obtained.
66,1 Teile Hydrochinon und 172,3 Teile Bis-(4-chlorphenyl-) sulfon werden in 900 Teilen N-Methylpyrrolidon und 300 Teilen Chlorbenzol gelöst, mit 87,2 Teilen wasserfreiem Kaliumcarbonat versetzt und wie in Beispiel 1 weiterbehandelt. Der erhaltene Polyäther besitzt eine reduzierte Viskosität von ηred = 1,1 und eine durchschnittliche Absorption von 6,2 %.66.1 parts of hydroquinone and 172.3 parts of bis (4-chlorophenyl) sulfone are dissolved in 900 parts of N-methylpyrrolidone and 300 parts of chlorobenzene, 87.2 parts of anhydrous potassium carbonate are added and the treatment is carried out as in Example 1. The polyether obtained has a reduced viscosity of η red = 1.1 and an average absorption of 6.2%.
Analog Beispiel 3 werden 66,1 Teile Resorcin zur Umsetzung verwendet. Das Polymere hat eine reduzierte Viskosität von ηred = 0,60 und eine durchschnittliche Absorption von 4,8 %.Analogously to Example 3, 66.1 parts of resorcinol are used for the reaction. The polymer has a reduced viscosity of η red = 0.60 and an average absorption of 4.8%.
Analog Beispiel 3 werden 111,7 Teile 4,4'-Dioxy-diphenyl eingesetzt. Man erhält einen Polyäther mit einer reduzierten Viskosität von ηred = 1,0 und einer durchschnittlichen Absorption von 8,0 %.Analogously to Example 3, 111.7 parts of 4,4'-dioxydiphenyl are used. A polyether with a reduced viscosity of η red = 1.0 and an average absorption of 8.0% is obtained.
150,2 Teile Bis-(4-oxyphenyl-)sulfon und 268,2 Teile 4,4'-Bis-(4-chlorbenzoyl-)diphenyläther werden in 900 Teilen Tetramethylensulfon (Sulfolan) und 300 Teilen Chlorbenzol gelöst und mit 87,2 Teilen wasserfreiem Kaliumcarbonat versetzt. Es wird dann wie in Beispiel 1 verfahren mit dem Unterschied, daß das Reaktionsgemisch iin der dritten Reaktionsstufe 12 Stunden bei 200°C gehalten wird. Nach der Aufarbeitung erhält man ein Polymeres mit einer reduzierten Viskosität von ηred = 0,40.150.2 parts of bis (4-oxyphenyl) sulfone and 268.2 parts of 4,4'-bis (4-chlorobenzoyl) diphenyl ether are dissolved in 900 parts of tetramethylene sulfone (sulfolane) and 300 parts of chlorobenzene and 87.2 Parts of anhydrous potassium carbonate are added. The procedure is then as in Example 1, with the difference that the reaction mixture is kept at 200 ° C. in the third reaction stage for 12 hours. After working up, a polymer is obtained with a reduced viscosity of η red = 0.40.
Claims (7)
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DE2731816 | 1977-07-14 | ||
DE19772731816 DE2731816A1 (en) | 1977-07-14 | 1977-07-14 | PROCESS FOR MANUFACTURING POLYAETHERS |
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EP0000361B1 EP0000361B1 (en) | 1984-05-16 |
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EP78100283A Expired EP0000361B1 (en) | 1977-07-14 | 1978-06-30 | Process for the preparation of poly(phenylene-oxy-phenylene-sulfone) |
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EP (1) | EP0000361B1 (en) |
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EP0029633A2 (en) * | 1978-09-05 | 1981-06-03 | Imperial Chemical Industries Plc | Polyarylethersulphone copolymers |
EP0030033A2 (en) * | 1979-12-03 | 1981-06-10 | Amoco Corporation | Aromatic polymers containing ketone groups |
EP0047999A1 (en) * | 1980-09-12 | 1982-03-24 | Amoco Corporation | Use of aromatic amorphous thermoplastic polymers for the production of molded articles |
EP0085185A1 (en) * | 1981-12-29 | 1983-08-10 | Amoco Corporation | Integrated process for the preparation of substantially linear high molecular weight thermoplastic polymers from aryl polyhalide monomers |
EP0113112A1 (en) * | 1982-12-23 | 1984-07-11 | Amoco Corporation | Use of an aromatic amorphous thermoplastic polymer |
EP0135941A2 (en) * | 1983-09-29 | 1985-04-03 | Amoco Corporation | Polyarylethersulfone polymer solution |
EP0146669A2 (en) * | 1983-04-18 | 1985-07-03 | Amoco Corporation | Improved poly(aryl ether)s |
EP0232019A2 (en) * | 1986-01-28 | 1987-08-12 | Imperial Chemical Industries Plc | Aromatic Polymer |
EP0234223A2 (en) * | 1986-01-24 | 1987-09-02 | BASF Aktiengesellschaft | Method for the preparation of aromatic block copolyethers |
US5049642A (en) * | 1988-12-23 | 1991-09-17 | Imperial Chemical Industries Plc | Aromatic polymers |
EP0702058A1 (en) | 1994-08-17 | 1996-03-20 | Basf Aktiengesellschaft | Moulding compositions of polyaryleneethers and copolyamides |
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- 1978-06-30 EP EP78100283A patent/EP0000361B1/en not_active Expired
- 1978-06-30 DE DE7878100283T patent/DE2862403D1/en not_active Expired
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EP0029633A2 (en) * | 1978-09-05 | 1981-06-03 | Imperial Chemical Industries Plc | Polyarylethersulphone copolymers |
EP0029633A3 (en) * | 1978-09-05 | 1981-08-05 | Imperial Chemical Industries Plc | Polyarylethersulphone copolymers |
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EP0085185A1 (en) * | 1981-12-29 | 1983-08-10 | Amoco Corporation | Integrated process for the preparation of substantially linear high molecular weight thermoplastic polymers from aryl polyhalide monomers |
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EP0135941A2 (en) * | 1983-09-29 | 1985-04-03 | Amoco Corporation | Polyarylethersulfone polymer solution |
EP0135941A3 (en) * | 1983-09-29 | 1986-02-05 | Union Carbide Corporation | Polyarylethersulfone polymer solution |
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EP0232019A2 (en) * | 1986-01-28 | 1987-08-12 | Imperial Chemical Industries Plc | Aromatic Polymer |
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Also Published As
Publication number | Publication date |
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DE2862403D1 (en) | 1984-06-20 |
DE2731816A1 (en) | 1979-02-01 |
EP0000361B1 (en) | 1984-05-16 |
US4200728A (en) | 1980-04-29 |
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