EP0000510B1 - Polyesters containing carbonate groups - Google Patents
Polyesters containing carbonate groups Download PDFInfo
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- EP0000510B1 EP0000510B1 EP78100380A EP78100380A EP0000510B1 EP 0000510 B1 EP0000510 B1 EP 0000510B1 EP 78100380 A EP78100380 A EP 78100380A EP 78100380 A EP78100380 A EP 78100380A EP 0000510 B1 EP0000510 B1 EP 0000510B1
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- 0 CCC(C)(CC)O*(C)[N+]([O-])O* Chemical compound CCC(C)(CC)O*(C)[N+]([O-])O* 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/64—Polyesters containing both carboxylic ester groups and carbonate groups
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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
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/66—Polyesters containing oxygen in the form of ether groups
Definitions
- the invention relates to aliphatic polyesters containing carbonate groups and a process for their production.
- Aliphatic polyesters can be produced by condensation of diols with dicarboxylic acids or dicarboxylic acid derivatives or by polycondensation of hydroxycarboxylic acids or lactones. They usually have relatively low molecular weights of up to a few thousand and can be used as diol components in the production of polyurethanes.
- polyester diols preferably with molecular weights Mn of 800, in particular from 1400 to about 3500
- bifunctional carbonic acid derivatives in as equimolar amounts as possible in vacuo (below 35 torr, preferred) at 25 to 1 torr) at a temperature between 100 ° C and 300 ° C, preferably 130 to 200 ° C, polycondensed in the presence of catalysts and the resulting condensation products are distilled off.
- Mn number average
- Reaction products of polyhydric alcohols with polyhydric aliphatic carboxylic acids are preferably those of dihydric and optionally additionally trihydric alcohols with preferably dihydric aliphatic carboxylic acids.
- their anhydrides or esters with lower alcohols or their mixtures can also be used.
- the polyvalent carboxylic acids are preferably acyclic. Examples include oxalic acid, malonic acid, succinic acid, adipic acid, suberic acid, azelaic acid, sebacic acid, hexahydrophthalic anhydride, glutaric anhydride.
- the polyhydric alcohols optionally in a mixture with one another, e.g. Ethylene glycol, propylene glycol- (1,2) and - (1,3, butylene glycol- (1,4) and - (2,3), hexanediol- (1,6), octanediol- (1,8), neopentylglycol, cyclohexanedimethanol , 1,4-bis (hydroxymethylcyclohexane), 2-methyl-1,3-propanediol, diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol and dibutylene glycol in question.
- Ethylene glycol propylene glycol- (1,2) and - (1,3, butylene glycol- (1,4) and - (2,3)
- hexanediol- (1,6), octanediol- (1,8) neopentylglycol
- the reaction products obtained from these carboxylic acids and alcohols are polyesters with terminal hydroxyl groups. They have molecular weights of approximately 800 to approximately 3500, they can be symbolized by the formula HO-X-OH, where X has the meaning given above.
- the polyesters according to the invention containing carbonate groups result from these polyesters with terminal hydroxyl groups by reaction with bifunctional carbonic acid aryl esters.
- Suitable catalysts for the reaction of the hydroxyl group-containing polyesters and the carbonic acid aryl esters are the transesterification catalysts, such as, for example, alkali metal or alkaline earth metal phenates, alkali metal or alkaline earth metal alcoholates and tertiary amines, such as, for example, triethylenediamine, morpholine, pyrrolidine, pyridine, triethylamine or zinc compounds, such as antimony trioxide and antioxidant trioxide Titanium tetrabutyl ester.
- the transesterification catalysts such as, for example, alkali metal or alkaline earth metal phenates, alkali metal or alkaline earth metal alcoholates and tertiary amines, such as, for example, triethylenediamine, morpholine, pyrrolidine, pyridine, triethylamine or zinc compounds, such as antimony trioxide and antioxidant trioxide Titanium tetrabutyl ester.
- the catalyst is used in amounts of 20 to 200 ppm, based on the total weight of the polycondensation components.
- the amount of catalyst can be fallen below if the starting products contain no basic impurities when using the acidic catalysts and no acidic impurities when using the basic catalysts;
- the smallest possible amounts of catalyst are preferred in order to avoid the product's inherent color.
- the reaction is preferably carried out in bulk, ie in the absence of solvents.
- solvents which are inert under the reaction conditions such as hydrocarbons, in particular aromatic hydrocarbons, can also be used.
- the reaction time depends on the reaction temperature, the type and amount of the catalyst used and on the desired molecular weight of the polyester containing carbonate groups. In general, 2 to 48 hours, preferably 4 to 24 hours, are sufficient.
- the resulting volatile condensation products can be removed during the reaction, by batchwise distillation, in continuous mode by fractional distillation.
- a mixture of polyester diol and bifunctional carbonic acid aryl ester, preferably diphenyl carbonate, or a mixture of diphenyl carbonate and compounds of the formula (11) is preferably polycondensed at 110 to 170 ° C. and then at 170 ° C. and higher by adding a bifunctional carbonic acid aryl ester to the sodium phenolate as catalyst Formula (11), preferably with n> 1, with simultaneous removal of volatile condensation products by distillation, increases the viscosity of the polycondensation mixture. It proved to be advantageous to carry out the polycondensation in high-viscosity reactors such as kneaders or screw machines.
- the polycondensation can be carried out in a known manner, e.g. can be ended by lowering the reaction temperature, destroying or removing the catalyst or by means of so-called stoppers. It has proven to be advantageous to use carboxylic acid aryl esters in the case of alcohol end groups and alcohols as stoppers in the case of aryl carbonate end groups. If bifunctional compounds are used as stoppers, it is possible to terminate the polycondensation with an increase in the average molecular weight if the dosage is precise.
- polyesters according to the invention can be used as polymeric plasticizers or additives for other plastics, their good rubber properties, aging resistance and excellent processability in a mixture with other plastics being particularly striking. Depending on the molecular weight and chemical composition, they can also be used as adhesives, sealing materials or for coating textiles.
- reaction mixture is dissolved after cooling 120 ° C in 1 liter of toluene, 20 parts by weight of the above polyester diol is added with thorough mixing and the toluene is then evaporated off in vacuo, slowly increasing the internal temperature of the reaction mixture to 220 ° C; at this temperature the reaction mixture is dried for 2 hours in a vacuum and careful evaporation of all volatile products.
- the colorless rubber-like material thus formed has a Staudinger index [ 1]] , measured in THF, of 1.35.
- the product a colorless, rubbery mass, has a Staudinger index [q], measured in THF, of 1.3.
Description
Die Erfindung betrifft Carbonatgruppen enthaltende aliphatische Polyester und ein Verfahren zu ihrer Herstellung. Aliphatische Polyester können durch Kondensation von Diolen mit Dicarbonsäuren oder Dicarbonsäurederivaten oder durch Polykondensation von Hydroxycarbonsäuren oder Lactonen hergestellt werden. Sie haben meist relativ niedrige Molekulargewichte bis zu einigen Tausend und können als Diolkomponenten bei der Herstellung von Polyurethanen verwendet werden. Es wurde gefunden, daß man Carbonatgruppen enthaltende aliphatische Polyester mit Molekulargewichten über 20 000 erhält, wenn man Polyesterdiole, bevorzugt mit Molekulargewichten Mn von 800, insbesondere von 1400 bis etwa 3500, mit bifunktionellen Kohlensäurederivaten in möglichst äquimolaren Mengen im Vakuum (unterhalb 35 Torr, bevorzugt bei 25 bis 1 Torr) bei einer Temperatur zwischen 100°C und 300°C, vorzugsweise 130 bis 200°C, in Gegenwart von Katalysatoren polykondensiert und die dabei entstehenden Kondensationsprodukte abdestilliert. Molekulargewichte sind hier und im folgenden immer das Zahlenmittel (Mn) des Molekulargewichts.The invention relates to aliphatic polyesters containing carbonate groups and a process for their production. Aliphatic polyesters can be produced by condensation of diols with dicarboxylic acids or dicarboxylic acid derivatives or by polycondensation of hydroxycarboxylic acids or lactones. They usually have relatively low molecular weights of up to a few thousand and can be used as diol components in the production of polyurethanes. It has been found that carbonate group-containing aliphatic polyesters with molecular weights above 20,000 are obtained if polyester diols, preferably with molecular weights Mn of 800, in particular from 1400 to about 3500, are obtained with bifunctional carbonic acid derivatives in as equimolar amounts as possible in vacuo (below 35 torr, preferred) at 25 to 1 torr) at a temperature between 100 ° C and 300 ° C, preferably 130 to 200 ° C, polycondensed in the presence of catalysts and the resulting condensation products are distilled off. Molecular weights here and below are always the number average (Mn) of the molecular weight.
Gegenstand der Erfindung sind somit Carbonatgruppen enthaltende Polyester, die aus wiederkehrenden Struktureinheiten der Formel
- X der Rest eines Umsetzungsproduktes eines mehrwertigen Alkohols mit einer mehrwertigen aliphatischen Carbonsäure mit einem Molekulargewicht von 800 bis 3500 ist,
- X' = X oder den Rest eines aliphatischen Polyäthers vom Molekulargewicht 800 bis 3500 darstellt,
- n ist = 0 oder 1 bis 10 und
- m eine Zahl > 20, bevorzugt 22 bis 100, bedeutet, wobei die Grenzviskosität in Tetrahydrofuran (Staudinger-Index) [η] 0,8 bis 2,5
- X is the remainder of a reaction product of a polyhydric alcohol with a polyhydric aliphatic carboxylic acid with a molecular weight of 800 to 3500,
- X '= X or the rest of an aliphatic polyether of molecular weight 800 to 3500,
- n is = 0 or 1 to 10 and
- m denotes a number> 20, preferably 22 to 100, the intrinsic viscosity in tetrahydrofuran (Staudinger index) [η] 0.8 to 2.5
Umsetzungsprodukte von mehrwertigen Alkoholen mit mehrwertigen aliphatischen Carbonsäuren sind bevorzugt solche von zweiwertigen und gegebenenfalls zusätzlich dreiwertigen Alkoholen mit vorzugsweise zweiwertigen aliphatischen Carbonsäuren. Anstelle der freien Carbonsäuren können auch deren Anhydride oder Ester mit niederen Alkoholen oder deren Gemische verwendet werden. Die mehrwertigen Carbonsäuren sind bevorzugt acyclisch. Als Beispiele seien genannt Oxalsäure, Malonsäure, Bernsteinsäure, Adipinsäure, Korksäure, Azelainsäure, Sebacinsäure, Hexahydrophthalsäureanhydrid, Glutarsäureanhydrid.Reaction products of polyhydric alcohols with polyhydric aliphatic carboxylic acids are preferably those of dihydric and optionally additionally trihydric alcohols with preferably dihydric aliphatic carboxylic acids. Instead of the free carboxylic acids, their anhydrides or esters with lower alcohols or their mixtures can also be used. The polyvalent carboxylic acids are preferably acyclic. Examples include oxalic acid, malonic acid, succinic acid, adipic acid, suberic acid, azelaic acid, sebacic acid, hexahydrophthalic anhydride, glutaric anhydride.
Als mehrwertige Alkohole kommen, gegebenenfalls im Gemisch miteinander, z.B. Äthylenglykol, Propylenglykol-(1,2) und -(1,3, Butylenglykol-(1,4) und -(2,3), Hexandiol-(1,6), Octandiol-(1,8), Neopentylglykol, Cyclohexandimethanol, 1,4-Bis-(hydroxymethylcyclohexan), 2-Methyl-1,3-propandiol, Diäthylenglykol, Triäthylenglykol, Tetraäthylenglykol, Dipropylenglykol und Dibutylenglykol in Frage.The polyhydric alcohols, optionally in a mixture with one another, e.g. Ethylene glycol, propylene glycol- (1,2) and - (1,3, butylene glycol- (1,4) and - (2,3), hexanediol- (1,6), octanediol- (1,8), neopentylglycol, cyclohexanedimethanol , 1,4-bis (hydroxymethylcyclohexane), 2-methyl-1,3-propanediol, diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol and dibutylene glycol in question.
Die aus diesen Carbonsäuren und Alkoholen erhaltenen Umsetzungsprodukte stellen Polyester mit endständigen Hydroxylgruppen dar. Sie haben Molekulargewichte von ca. 800 bis ca. 3500, sie können durch die Formel HO-X-OH symbolisiert werden, wobei X die oben angegebene Bedeutung hat. Wie bereits angegeben, entstehen die erfindungsgemäßen Carbonatgruppen enthaltenden Polyester aus diesen Polyestern mit endständigen Hydroxylgruppen durch Umsetzung mit bifunktionellen Kohlensäurearylestern.The reaction products obtained from these carboxylic acids and alcohols are polyesters with terminal hydroxyl groups. They have molecular weights of approximately 800 to approximately 3500, they can be symbolized by the formula HO-X-OH, where X has the meaning given above. As already stated, the polyesters according to the invention containing carbonate groups result from these polyesters with terminal hydroxyl groups by reaction with bifunctional carbonic acid aryl esters.
Bifunktionelle Kohlensäurearylester sind insbesondere die der Formel (11)
- Ar ein substituierter oder unsubstituierter Arylrest mit 6 bis 18 C-Atomen, vorzugsweise mit 6 C-Atomen, ist,
- n = 0 oder 1 bis 10 ist und
- X' der bivalente Rest eines Polyesters oder Polyäthers, wie weiter oben definiert.
Solche Verbindungen sind bekannt.Bifunctional carbonic acid aryl esters are especially those of the formula (11)
- Ar is a substituted or unsubstituted aryl radical having 6 to 18 carbon atoms, preferably having 6 carbon atoms,
- n = 0 or 1 to 10 and
- X 'is the divalent radical of a polyester or polyether as defined above.
Such connections are known.
Zur Umsetzung der Hydroxylgruppen enthaltenden Polyester und der Kohlensäurearylester sind geeignete Katalysatoren die Umesterungskatalysatoren, wie beispeilsweise Alkali- oder Erdalkaliphenolate, Alkali- oder Erdalkalialkoholate und tertiäre Amine, wie beispielsweise Triäthylendiamin, Morpholin, Pyrrolidin, Pyridin, Triäthylamin oder Metallverbindungen wie Antimontrioxid, Zinkchlorid, Titantetrachlorid und Titansäuretetrabutylester.Suitable catalysts for the reaction of the hydroxyl group-containing polyesters and the carbonic acid aryl esters are the transesterification catalysts, such as, for example, alkali metal or alkaline earth metal phenates, alkali metal or alkaline earth metal alcoholates and tertiary amines, such as, for example, triethylenediamine, morpholine, pyrrolidine, pyridine, triethylamine or zinc compounds, such as antimony trioxide and antioxidant trioxide Titanium tetrabutyl ester.
Der Katalysator wird in Mengen von 20 bis 200 ppm, bezogen auf das Gesamtgewicht der Polykondensationskomponenten, verwendet. Die Katalysatormengen können unterschritten werden, wenn die Ausgangsprodukte bei Verwendung der sauren Katalysatoren keine basischen, bei Verwendung der basischen Katalysatoren keine sauren Verunreinigungen enthalten; möglichst geringe Katalysatormengen sind bevorzugt, um Eigenfarbe der Produkte zu vermeiden.The catalyst is used in amounts of 20 to 200 ppm, based on the total weight of the polycondensation components. The amount of catalyst can be fallen below if the starting products contain no basic impurities when using the acidic catalysts and no acidic impurities when using the basic catalysts; The smallest possible amounts of catalyst are preferred in order to avoid the product's inherent color.
Vorzugsweise wird in Substanz umgesetzt, also in Abwesenheit von Lösungsmitteln. Es können jedoch auch unter den Reaktionsbedingungen inerte Lösungsmittel wie Kohlenwasserstoffe, insbesondere aromatische Kohlenwasserstoffe, verwendet werden.The reaction is preferably carried out in bulk, ie in the absence of solvents. However, solvents which are inert under the reaction conditions, such as hydrocarbons, in particular aromatic hydrocarbons, can also be used.
Die Reaktionszeit richtet sich nach der Reaktionstemperatur, der Art und Menge des verwendeten Katalysators und nach dem gewünschten Molekulargewicht des Carbonatgruppen enthaltenden Polyesters. Im allgemeinen genügen 2 bis 48 Stunden, vorzugsweise 4 bis 24 Stunden.The reaction time depends on the reaction temperature, the type and amount of the catalyst used and on the desired molecular weight of the polyester containing carbonate groups. In general, 2 to 48 hours, preferably 4 to 24 hours, are sufficient.
Die entstehenden flüchtigen Kondensationsprodukte können während der Reaktion entfernt werden, bei diskontinuierlicher Verfahrensweise destillative, bei kontinuierlicher Verfahrensweise durch fraktionierte Destillation. Bevorzugt wird mit Natriumphenolat als Katalysator eine Mischung aus Polyesterdiol und bifunktionellem Kohlensäurearylester, vorzugsweise Diphenylcarbonat, oder eine Mischung aus Diphenylcarbonat und Verbindungen der Formel (11) bei 110 bis 170°C polykondensiert und anschließend bei 170°C und höher durch Zufügen eines bifunktionellen Kohlensäurearylesters der Formel (11), bevorzugt mit n > 1, unter gleichzeitiger destillativer Abtrennung flüchtiger Kondensationsprodukte die Viskosität des Polykondensationsgemischs erhöht. Es erwies sich als günstig, die Polykondensation in Hochviskos-Reaktoren wie Knetern oder Schneckenmaschinen durchzuführen.The resulting volatile condensation products can be removed during the reaction, by batchwise distillation, in continuous mode by fractional distillation. A mixture of polyester diol and bifunctional carbonic acid aryl ester, preferably diphenyl carbonate, or a mixture of diphenyl carbonate and compounds of the formula (11) is preferably polycondensed at 110 to 170 ° C. and then at 170 ° C. and higher by adding a bifunctional carbonic acid aryl ester to the sodium phenolate as catalyst Formula (11), preferably with n> 1, with simultaneous removal of volatile condensation products by distillation, increases the viscosity of the polycondensation mixture. It proved to be advantageous to carry out the polycondensation in high-viscosity reactors such as kneaders or screw machines.
Die Polykondensation kann in bekannter Weise, z.B. durch Absenken der reaktionstemperatur, Vernichten oder Entfernen des Katalysators oder durch sogenannte Stopper beendet werden. So hat es sich als vorteilhaft erwiesen, im Falle von Alkoholendgruppen Carbonsäurearylester und im Falle von Arylcarbonatendgruppen Alkohole als Stopper einzusetzen. Verwendet man bifunktionelle Verbindungen als Stopper, so ist es möglich, bei genauer Dosierung ein Abbrechen der Polykondensation unter Erhöhung des durchschnittlichen Molekulargewichtes zu erreichen.The polycondensation can be carried out in a known manner, e.g. can be ended by lowering the reaction temperature, destroying or removing the catalyst or by means of so-called stoppers. It has proven to be advantageous to use carboxylic acid aryl esters in the case of alcohol end groups and alcohols as stoppers in the case of aryl carbonate end groups. If bifunctional compounds are used as stoppers, it is possible to terminate the polycondensation with an increase in the average molecular weight if the dosage is precise.
Die erfindungsgemäßen Polyester können als polymere Weichmacher oder Zusatzstoffe für andere Kuntstoffe verwendet werden, wobei ihre gute Kautschukeigenschaft, Alterungsbeständigkeit und hervorragende Verarbeitbarkeit im Gemisch mit anderen Kunststoffen besonders auffallend sind. Sie können auch je nach Molekulargewicht und chemischer Zusammensetzung als Klebstoffe, Dichtungsmaterialien oder zur Beschichtung von Textilien Verwendung finden.The polyesters according to the invention can be used as polymeric plasticizers or additives for other plastics, their good rubber properties, aging resistance and excellent processability in a mixture with other plastics being particularly striking. Depending on the molecular weight and chemical composition, they can also be used as adhesives, sealing materials or for coating textiles.
Die Grenzviskosität (Staudinger-Index) [1]] wurde in Tetrahydrofuran bei 25°C gemessen und ist in
2000 Gew.-Teile eines Polyesterdiols aus Adipinsäure und einer Mischung aus n-Hexan-1,6- diol/Neopentylglykol im Verhältnis 65/35 vom mittleren Molekulargewicht Mn 2000 (bestimmt durch OH-Zahl-Messung), 214 Gew.-Teile Diphenylcarbonat und 0,12 Gew.-Teile Natriumphenolat werden unter Rühren und einem Vakuum von 1,5 Torr 2 Stunden bei 130°C und 1 Stunde bei 150°C gerührt, wobei man flüchtige Polykondensationsprodukte, die zum größten Teil aus Phenol bestehen, abdestilliert. Unter fortgesetzter Destillation steigert man die Temperatur für 4 Stunden auf 180°C; während dieser Zeit werden 20 Gew.-Teile eines über -OCOO-Brücken verlängerten Polytetrahydrofurandiols mit Phenylcarbonatendgruppen (Mn des Polytetrahydrofuran 2000, Verlängerungsgrad gleich 2) zudosiert, anschließend steigert man unter langsamem Rühren oder Kneten die Reaktionstemperatur auf circa 185 bis 190°C für 5 Stunden. Das Produkt, eine farblose kautschukartige Masse, besitzt einen Staudinger-Index [17], gemessen in THF, von 1,5.2000 parts by weight of a polyester diol from adipic acid and a mixture of n-hexane-1,6-diol / neopentyl glycol in a ratio of 65/35 of the average molecular weight Mn 2000 (determined by OH number measurement), 214 parts by weight of diphenyl carbonate and 0.12 parts by weight of sodium phenolate are stirred with stirring and a vacuum of 1.5 torr at 130 ° C. for 2 hours and at 150 ° C. for 1 hour, volatile polycondensation products, which largely consist of phenol, being distilled off. With continued distillation, the temperature is raised to 180 ° C. for 4 hours; During this time, 20 parts by weight of a polytetrahydrofuran diol with phenyl carbonate end groups (Mn of polytetrahydrofuran 2000, degree of elongation equal to 2) extended via -OCOO bridges are metered in, then the reaction temperature is raised to about 185 to 190 ° C. for 5 with slow stirring or kneading Hours. The product, a colorless rubbery mass, has a Staudinger index [17], measured in THF, of 1.5.
1800 Gew.-Teile eines Polyesterdiols aus Adipinsäure und n-Hexan-1,6-diol vom mittleren Molekulargewicht Mn 1800 (bestimmt durch OH-Zahl-Messung), 214 Gew.-Teile Diphenylcarbonat und 0,11 Gew.-Teile Natriumphenolat werden unter Rühren und einem Vakuum von 0,5 Torr 2 Stunden bei 130°C und 1 Stunde bei 150°C gerührt, wobei man flüchtige Polykondensationsprodukte, die zum größten Teil aus Phenol bestehen, abdestilliert. Unter fortgesetzter Destillation steigert man die Temperatur für 4 Stunden auf 180°C; während dieser Zeit werden 35 Gew.-Teile eines über -OCOO Brücken verlängerten Polyesterdiols mit Phenylcarbonatendgruppen (
1000 Gew.-Teile eines Polyesterdiols aus Adipinsäure und einer Mischung aus n-Hexan-1,6- diol/Neopentylglykol im Verhältnis 65/35 vom mittleren Molekulargewicht Mn 2000 (bestimmt durch OH-Zahl-Messung), 107 Gew.-Teile Diphenylcarbonat und 0,12 Gew.-Teile Neatriumphenolat werden unter Rühren und einem Vakuum von 1,5 Torr 2 Stunden bei 130°C und 1/2 Stunde bei 150°C gerührt, wobei man flüchtige Kondensationsprodukte, die zum größten Teil aus Phenol bestehen, abdestilliert. Nach Abkühlen des Gemisches auf 130°C fügt man eine Mischung aus 900 Gew.-Teilen eines Polyesterdiols aus Adipinsäure und n-Hexan-1,6-diol vom mittleren Molekulargewicht Mn von 1800 (bestimmt durch OH-Zahl-Messung) und 107 Gew.-Teile Diphenylcarbonat hinzu. Anschließend rührt man 2 Stunden bei 130°C und 2 Stunden bei 160°C unter fortwährender Abdestillation flüchtiger Produkte; man steigert die Temperatur für 4 Stunden auf 180C; während dieser Zeit werden 22 Gew.-Teile eines über -OCCO-Brücken verlängerten Polytetrahydrofurandiols mit Phenylcarbonatendgruppen (Mn des Polytetrahydrofurandiols 2000, Verlängerungsgrad 2) zudosiert; anschließend steigert man unter langsamem Rühren oder Kneten die Reaktionstemperatur für 2 Stunden auf 185°C und für 4 Stunden auf 200°C.1000 parts by weight of a polyester diol from adipic acid and a mixture of n-hexane-1,6-diol / neopentyl glycol in a ratio of 65/35 from the average molecular weight Mn 2000 (determined by OH number measurement), 107 parts by weight of diphenyl carbonate and 0.12 part by weight of neatrium phenolate are stirred with stirring and a vacuum of 1.5 torr for 2 hours at 130 ° C. and 1/2 hour at 150 ° C., volatile condensation products, which largely consist of phenol, distilled off. After the mixture has cooled to 130 ° C., a mixture of 900 parts by weight of a polyester diol from adipic acid and n-hexane-1,6-diol with an average molecular weight Mn of 1,800 (determined by OH number measurement) and 107 parts by weight are added Add parts of diphenyl carbonate. The mixture is then stirred at 130 ° C. for 2 hours and at 160 ° C. for 2 hours while volatile products are continuously distilled off; the temperature is raised to 180C for 4 hours; 22 parts by weight of a polytetrahydrofuran diol with phenyl carbonate end groups (Mn of the polytetrahydrofuran diol 2000, degree of elongation 2) extended via -OCCO bridges are metered in during this time; the reaction temperature is then increased to 185 ° C. for 2 hours and to 200 ° C. for 4 hours with slow stirring or kneading.
Das Produkt, eine farblose kautschukartige Masse, besitzt einen Staudinger-Index [q], gemessen in THF, von 1,3.The product, a colorless, rubbery mass, has a Staudinger index [q], measured in THF, of 1.3.
2000 Gew.-Teile eines Polyesterdiols aus Adipinsäure und einer Mischung aus n-Hexan-1,6- diol/Neopentylglykol im Verhältnis 65:35 vom mittleren Molekulargewicht
Claims (1)
having an intrinsic viscosity in tetrahydrofuran of from 0.8 to 2.5
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19772732718 DE2732718A1 (en) | 1977-07-20 | 1977-07-20 | POLYESTER CONTAINING CARBONATE GROUPS |
| DE2732718 | 1977-07-20 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP0000510A1 EP0000510A1 (en) | 1979-02-07 |
| EP0000510B1 true EP0000510B1 (en) | 1980-09-03 |
Family
ID=6014355
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP78100380A Expired EP0000510B1 (en) | 1977-07-20 | 1978-07-12 | Polyesters containing carbonate groups |
Country Status (5)
| Country | Link |
|---|---|
| US (1) | US4192940A (en) |
| EP (1) | EP0000510B1 (en) |
| JP (1) | JPS5422494A (en) |
| DE (2) | DE2732718A1 (en) |
| IT (1) | IT1106853B (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2823161A1 (en) * | 1978-05-26 | 1979-11-29 | Bayer Ag | SOFTENED VINYL CHLORIDE POLYMERISATE |
| US4506045A (en) * | 1982-10-02 | 1985-03-19 | Bayer Aktiengesellschaft | Cellulose ester-aliphatic polycarbonate thermoplastic moulding compositions |
| DE3316851A1 (en) * | 1983-05-07 | 1984-11-08 | Bayer Ag, 5090 Leverkusen | POLYMERIZABLE DENTAL MEASURES AND DENTAL MOLDED BODIES MADE THEREOF |
| DE3322667A1 (en) * | 1983-06-23 | 1985-01-10 | Bayer Ag, 5090 Leverkusen | METHOD FOR PRODUCING HIGH MOLECULAR POLYESTER CARBONATES |
| DE3932949A1 (en) * | 1989-10-03 | 1991-04-11 | Bayer Ag | ELASTIC FIBERS HIGH EXPANSABILITY AND STRENGTH AND A METHOD FOR THEIR PRODUCTION |
| US5654380A (en) * | 1994-05-23 | 1997-08-05 | Mitsubishi Gas Chemical Company, Inc. | Aliphatic polyester carbonate and process for producing the same |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE1495626B1 (en) * | 1960-03-30 | 1971-06-09 | Bayer Ag | METHOD OF MANUFACTURING POLYESTERS |
| DE1301552B (en) * | 1963-06-19 | 1969-08-21 | Teijin Ltd | Process for the production of linear polyesters |
| FR1401635A (en) * | 1964-06-19 | 1965-06-04 | Teijin Ltd | Process for the preparation of essentially linear polyesters |
| DE1964998C3 (en) * | 1969-12-24 | 1979-02-15 | Bayer Ag, 5090 Leverkusen | Process for the production of polyurethane elastomers |
| DE2651639A1 (en) * | 1976-11-12 | 1978-05-24 | Bayer Ag | PROCESS FOR THE PRODUCTION OF CARBON ESTERS FROM POLYESTER POLYOLS |
| DE2712435A1 (en) * | 1977-03-22 | 1978-09-28 | Bayer Ag | PROCESS FOR THE PREPARATION OF CARBONATE ARYLESTERS FROM POLYESTERDIOLS EXTENDED VIA CARBONATE GROUPS |
-
1977
- 1977-07-20 DE DE19772732718 patent/DE2732718A1/en not_active Withdrawn
-
1978
- 1978-07-12 EP EP78100380A patent/EP0000510B1/en not_active Expired
- 1978-07-12 DE DE7878100380T patent/DE2860136D1/en not_active Expired
- 1978-07-14 US US05/924,708 patent/US4192940A/en not_active Expired - Lifetime
- 1978-07-18 IT IT50345/78A patent/IT1106853B/en active
- 1978-07-18 JP JP8682178A patent/JPS5422494A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| US4192940A (en) | 1980-03-11 |
| JPS6256173B2 (en) | 1987-11-24 |
| EP0000510A1 (en) | 1979-02-07 |
| DE2732718A1 (en) | 1979-02-15 |
| IT1106853B (en) | 1985-11-18 |
| IT7850345A0 (en) | 1978-07-18 |
| JPS5422494A (en) | 1979-02-20 |
| DE2860136D1 (en) | 1980-12-11 |
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