EP0000510A1 - Polyesters containing carbonate groups - Google Patents

Polyesters containing carbonate groups Download PDF

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Publication number
EP0000510A1
EP0000510A1 EP78100380A EP78100380A EP0000510A1 EP 0000510 A1 EP0000510 A1 EP 0000510A1 EP 78100380 A EP78100380 A EP 78100380A EP 78100380 A EP78100380 A EP 78100380A EP 0000510 A1 EP0000510 A1 EP 0000510A1
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Prior art keywords
weight
molecular weight
hours
diol
carbonate groups
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German (de)
French (fr)
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EP0000510B1 (en
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Christian Dr. Lindner
Carlhans Dr Süling
Herbert Dr Bartl
Dietrich Dr. Hardt
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Bayer AG
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Bayer AG
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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
    • C08G63/64—Polyesters containing both carboxylic ester groups and carbonate groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • 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 carbonate group-containing aliphatic polyesters and a process for their preparation.
  • Aliphatic polyesters can be prepared by condensing diols with dicarboxylic acids or dicarboxylic acid derivatives or by polycondensing 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 carbonic acid, oxalic acid, malonic acid, succinic acid, adipic acid, suberic acid, azelaic acid, sebacic acid, hexahydrophthalic anhydride, glutaric anhydride.
  • the reaction products obtained from these carboxylic acids and alcohols are polyesters with terminal hydroxyl groups. They have molecular weights from about 800 to about 3500, they can be symbolized by the formula HQ-X-OH, where X has the meaning given above.
  • the polyesters according to the invention containing carbonate groups are formed 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 or alkaline earth phenolates, alkali or alkaline earth alcoholates and tertiary amines, such as, for example, triethylenediamine, morpholine, pyrrolidine, pyridine, triethylamine or metal compounds such as antimony trioxide, zinc chloride Titanium tetrabutyl ester.
  • the transesterification catalysts such as, for example, alkali or alkaline earth phenolates, alkali or alkaline earth alcoholates and tertiary amines, such as, for example, triethylenediamine, morpholine, pyrrolidine, pyridine, triethylamine or metal compounds such as antimony trioxide, zinc chloride 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 undercut 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 distillation in the case of a batchwise procedure, or in the case of a continuous procedure wise 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 (II) is preferably polycondensed at 110 to 170 ° C. and then at 170 ° C. and higher by adding a bifunctional carbonic acid aryl ester of the sodium phenolate as catalyst Formula (II), 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. by lowering the reaction temperature, destroying or removing the catalyst or by so-called stoppers. It has proven to be advantageous to use aryl carboxylates 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 loading layering of textiles.
  • a polyester diol with phenyl carbonate end groups (Mn of the polyester diol 2150, consisting of adipic acid and n-hexane-1,6-diol, degree of elongation equal to 2), extended over -OCOO bridges, are metered in, followed by a slow increase Stir or knead the reaction temperature aftur at 190 ° C for 4 hours, then dissolves the reactive mixture by cooling to 120 ° C in 1 liter of toluene, adds 20 parts by weight of the above-mentioned polyester diol with thorough mixing and then evaporates the toluene in vacuo, slowly the internal temperature of the reaction mixture increases 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 [ ⁇ ], measured in THF, of 1.35.
  • a mixture of 900 parts by weight of a polyester diol of adipic acid and n-hexane-1,6-diol of average molecular weight is added M n of 1800 (determined by OH number measurement) and 107 parts by weight of diphenyl carbonate.
  • M n 1800 (determined by OH number measurement) and 107 parts by weight of diphenyl carbonate.
  • the mixture is then stirred at 13 ° C. for 2 hours and at 160 ° C. for 2 hours, with continuous distillation of volatile products; the temperature is raised to 180 ° C.
  • the product a colorless rubbery mass, has a -Index [ ⁇ ] gemesing in from 1.3.

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

Abstract

Carbonatgruppen enthaltende Polyester, die aus wiederkehrenden Strucktureinheiten der Formel <IMAGE> aufgebaut sind, in der X den Rest eines Umsetzungsproduktes eines mehrwertigen Alkohols mit einer mehrwertigen aliphatischen Carbonsäure mit einem Molekulargewicht von 800 bis 3500, X' = X oder den Rest eines aliphatischen Polyäthers vom Molekulargewicht 800 bis 3500 darstellt, n = 0 oder 1 bis 10 und m eine Zahl > 20 bedeutet, wobei die Grenzviskosität im Tetrahydrofuran 0,8 bis 2,5 (dl/g) ist.Polyesters containing carbonate groups, which are composed of recurring structural units of the formula <IMAGE>, in which 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 remainder of an aliphatic polyether of Molecular weight is 800 to 3500, n = 0 or 1 to 10 and m is a number> 20, the intrinsic viscosity in tetrahydrofuran being 0.8 to 2.5 (dl / g).

Description

Die Erfindung betrifft Carbonatgruppen enthaltehde 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 carbonate group-containing aliphatic polyesters and a process for their preparation. Aliphatic polyesters can be prepared by condensing diols with dicarboxylic acids or dicarboxylic acid derivatives or by polycondensing 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

Figure imgb0001
aufgebaut sind, in der

  • 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] 7 0,8 bis 2,5
    Figure imgb0002
     ist.
The invention thus relates to polyesters containing carbonate groups, which consist of recurring structural units of the formula
Figure imgb0001
 are built in the
  • 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] 7 0.8 to 2.5
    Figure imgb0002
     is.

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 Kohlensäure, 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 carbonic acid, oxalic acid, malonic acid, succinic acid, adipic acid, suberic acid, azelaic acid, sebacic acid, hexahydrophthalic anhydride, glutaric anhydride.

Als mehrweig Alkohole kommen, gegebenenfails im Cemisch 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.When several alcohols come, if necessary in a mixture with each other, 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 HQ-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 from about 800 to about 3500, they can be symbolized by the formula HQ-X-OH, where X has the meaning given above. As already stated, the polyesters according to the invention containing carbonate groups are formed from these polyesters with terminal hydroxyl groups by reaction with bifunctional carbonic acid aryl esters.

Bifunktionelle Kohlensäurearylester sind insbesondere die der Formel (II)

Figure imgb0003
worin .

  • Ar ein substituierter oder unsubstituierter Arylrest mit 6 bis 18 C-Atomen, vorzugsweise mit 6 C-Atomen,ist,
  • n = O 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, in particular, those of the formula (II)
Figure imgb0003
 in which.
  • Ar is a substituted or unsubstituted aryl radical having 6 to 18 carbon atoms, preferably having 6 carbon atoms,
  • n = O 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 beispielsweise 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 or alkaline earth phenolates, alkali or alkaline earth alcoholates and tertiary amines, such as, for example, triethylenediamine, morpholine, pyrrolidine, pyridine, triethylamine or metal compounds such as antimony trioxide, zinc chloride 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 undercut 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 destillativ, bei kontinuierlicher Verfahrenarweise 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 (II) bei 110 bis 170°C polykondensiert und anschließend bei 170°C und höher durch Zufügen eines bifunktionellen Kohlensäurearylesters der Formel (II),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 distillation in the case of a batchwise procedure, or in the case of a continuous procedure wise 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 (II) is preferably polycondensed at 110 to 170 ° C. and then at 170 ° C. and higher by adding a bifunctional carbonic acid aryl ester of the sodium phenolate as catalyst Formula (II), 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. by lowering the reaction temperature, destroying or removing the catalyst or by so-called stoppers. It has proven to be advantageous to use aryl carboxylates 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 Kunststoffe 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 loading layering of textiles.

Die Grenzviskosität (Staudinger-Index) [η] wurde in Tetrahydrofuran bei 25°C gemessen und ist in

Figure imgb0004
gangegeben. Zur Definition s. H.G. Elias "Makromoleküle", Hüthig % Wepf-Verlag, Basel, Seite 265.The intrinsic viscosity (Staudinger index) [η] was measured in tetrahydrofuran at 25 ° C and is in
Figure imgb0004
 given. For definition see HG Elias "Macromolecules", Hüthig% Wepf-Verlag, Basel, page 265.

Beispiel 1example 1

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 (gn 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 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 average molecular weight M n 2000 (determined by OH number measurement), 214 parts by weight of diphenyl carbonate and 0.12 part by weight of sodium phenolate are stirred for 2 hours at 130 ° C. and 1 hour at 150 ° with a vacuum of 1.5 torr C stirred, while distilling off volatile polycondensation products, which largely consist of phenol. 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 ( g n of polytetrahydrofuran 2000, degree of elongation equal to 2) extended over -OCOO bridges are metered in, then the reaction temperature is raised to about 185 to 190 ° C. with slow stirring or kneading 5 hours. The product, a colorless rubbery mass, has a Staudinger index, measured in THF, of 1.5.

Beispiel 2Example 2

1800 Gew.-Teile eines Polyesterdiols aus Adipinsäure und n-Hexan-1,6-diol vom mittleren Molekulargewicht Mn1800 (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 (Mn des Polyesterdiols 2150, bestehend aus Adipinsäure und n-Hexan-1,6-diol, Verlängerungsgrad gleich 2) zudosiert, anschließend steigert man unter langsamem Rühren oder Kneten die Reaktionstempe-
aftur auf 190°C für 4 Stunden, löst dann das Reakticnsgemisch sch Abkühlen auf 120°C in 1 Liter Toluol, fügt unter guter Durchmischung 20 Gew.-Teile des oben genannten Polyesterdiols hinzu und dampft nun das Toluol im Vakuum ab, wobei man langsam die Innentemperatur des Reaktionsgemisches auf 220°C steigert; bei dieser Temperatur wird das Reaktionsgemisch 2 Stunden im Vakuum und sorgfältigem Abdampfen aller flüchtigen Produkte getrocknet. Das so gebildete farblose kautschukartige Material besitst einen Staudinger-Index [η], gemessen in THF, von 1,35.1800 parts by weight of a polyester diol from adipic acid and n-hexane-1,6-diol of average molecular weight Mn1800 (determined by OH number measurement), 214 parts by weight of diphenyl carbonate and 0.11 part by weight of sodium phenolate Stirring and a vacuum of 0.5 Torr for 2 hours at 130 ° C and 1 hour at 150 ° C, while distilling volatile polycondensation products, which largely consist of phenol. With continued distillation, the temperature is raised to 180 ° C. for 4 hours; During this time, 35 parts by weight of a polyester diol with phenyl carbonate end groups (Mn of the polyester diol 2150, consisting of adipic acid and n-hexane-1,6-diol, degree of elongation equal to 2), extended over -OCOO bridges, are metered in, followed by a slow increase Stir or knead the reaction temperature
aftur at 190 ° C for 4 hours, then dissolves the reactive mixture by cooling to 120 ° C in 1 liter of toluene, adds 20 parts by weight of the above-mentioned polyester diol with thorough mixing and then evaporates the toluene in vacuo, slowly the internal temperature of the reaction mixture increases 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 [η], measured in THF, of 1.35.

Beispiel 3Example 3

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 Natriumphenolat 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-l,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 13C°C und 2 Stunden bei 160°C unter fortwährender Abaestillation flüchtiger Produkte; man steigert die Temperatur für 4 Stunden auf 180°C; während dieser Zeit werden 22 Gew.-Teile eines über -OCCO-Brücken verlängerten Folytetrahydrofurandiols mit Phenylcarbonatendgruppen (Mn des Polytetrahydrofurandiols 2000, Verlängerungsgrad 2) zudosiert; anschließend doeigert man unter langsamem Rühren oder Kneten die Reaktions-

Figure imgb0005
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 of average molecular weight M n 2000 (determined by OH number measurement), 107 parts by weight of diphenyl carbonate and 0.12 part by weight of sodium phenolate are stirred for 2 hours at 130 ° C. and 1/2 hour with stirring and a vacuum of 1.5 torr Stirred 150 ° C, while distilling off volatile condensation products, which largely consist of phenol. After the mixture has cooled to 130 ° C., a mixture of 900 parts by weight of a polyester diol of adipic acid and n-hexane-1,6-diol of average molecular weight is added M n of 1800 (determined by OH number measurement) and 107 parts by weight of diphenyl carbonate. The mixture is then stirred at 13 ° C. for 2 hours and at 160 ° C. for 2 hours, with continuous distillation of volatile products; the temperature is raised to 180 ° C. for 4 hours; during this time, 22 parts by weight of a folytetrahydrofuran diol with phenyl carbonate end groups ( M n of the polytetrahydrofuran diol 2000, degree of extension 2) metered in; then the reaction is carried out with slow stirring or kneading
Figure imgb0005
for 2 hours at 185 ° C and for 4 hours at 200 ° C.

as Produkt, eine farblose kautschukartige Masse, besitzt eine

Figure imgb0006
-Index [η] gemesing in von 1,3.The product, a colorless rubbery mass, has a
Figure imgb0006
-Index [η] gemesing in from 1.3.

Beispiel 4Example 4

2000 Gew.-Teile eines Polyesterdiols aus Adipinsäure und einer Mischung aus n-Hexan-1,6-diol/Neopentylglykol im Verhältnis 65 : 35 vom mittleren Molekulargewicht M n 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 größtenteils aus Phenol bestehen, abdestilliert: Unter festgesetzter Destillation steigert man die Temperatur für 6 Stunden auf 180°C und 2 Stunden auf 195°C. Das so erhaltene Produkt, eine farblose kautschukartige weiche Masse, besitzt einen Staudinger-Index [η], gemessen in THF, von 0,8.2000 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 by average molecular weight M n 2000 (determined by OH number measurement), 214 parts by weight of diphenyl carbonate and 0.12 part by weight of sodium phenolate are stirred for 2 hours at 130 ° C. and 1 hour at 150 ° with a vacuum of 1.5 torr C stirred, whereby volatile polycondensation products, which consist largely of phenol, are distilled off: With fixed distillation, the temperature is raised to 180 ° C. for 6 hours and to 195 ° C. for 2 hours. The product obtained in this way, a colorless, rubber-like, soft mass, has a Staudinger index [η], measured in THF, of 0.8.

Claims (1)

Carbonatgruppen enthaltende Polyester,die aus wiederkehrenden Struktureinheiten der Formel
Figure imgb0007
aufgebaut sind, in der X den Rest eines Umsetzungsproduktes eines mehrwertigen Alkohols mit einer mehrwertigen aliphatischen Carbonsäure mit einem Molekulargewicht von 800 bis 3500, X' = X oder den Rest eines aliphatischen Polyäthers vom Molekulargewicht 800 bis 3500 darstellt, n = 0 oder 1 bis 10 und m eine Zahl > 20 bedeutet,
wobei die Grenzviskosität im Tetrahydrofuran 0,8 bis 2,5 dl ist.Polyesters containing carbonate groups, which consist of recurring structural units of the formula
Figure imgb0007
 are built in the 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 = 0 or 1 to 10 and m means a number> 20,
the intrinsic viscosity in tetrahydrofuran is 0.8 to 2.5 d l .
EP78100380A 1977-07-20 1978-07-12 Polyesters containing carbonate groups Expired EP0000510B1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE2732718 1977-07-20
DE19772732718 DE2732718A1 (en) 1977-07-20 1977-07-20 POLYESTER CONTAINING CARBONATE GROUPS

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EP0000510A1 true EP0000510A1 (en) 1979-02-07
EP0000510B1 EP0000510B1 (en) 1980-09-03

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JP (1) JPS5422494A (en)
DE (2) DE2732718A1 (en)
IT (1) IT1106853B (en)

Cited By (4)

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EP0005736A1 (en) * 1978-05-26 1979-12-12 Bayer Ag Plasticized PVC compositions
EP0131164A1 (en) * 1983-06-23 1985-01-16 Bayer Ag Process for the preparation of high molecular polyester carbonates
EP0421217A2 (en) * 1989-10-03 1991-04-10 Bayer Ag Elasthan fibres with high elasticity and tenacity and process for their preparation
EP0684270A2 (en) * 1994-05-23 1995-11-29 Mitsubishi Gas Chemical Company, Inc. Aliphatic polyester carbonate and process for producing the same

Families Citing this family (2)

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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

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FR1401635A (en) * 1964-06-19 1965-06-04 Teijin Ltd Process for the preparation of essentially linear polyesters
DE1964998A1 (en) * 1969-12-24 1971-07-01 Bayer Ag Process for the production of polyurethane elastomers

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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
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

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FR1401635A (en) * 1964-06-19 1965-06-04 Teijin Ltd Process for the preparation of essentially linear polyesters
DE1964998A1 (en) * 1969-12-24 1971-07-01 Bayer Ag Process for the production of polyurethane elastomers

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0005736A1 (en) * 1978-05-26 1979-12-12 Bayer Ag Plasticized PVC compositions
EP0131164A1 (en) * 1983-06-23 1985-01-16 Bayer Ag Process for the preparation of high molecular polyester carbonates
EP0421217A2 (en) * 1989-10-03 1991-04-10 Bayer Ag Elasthan fibres with high elasticity and tenacity and process for their preparation
EP0421217A3 (en) * 1989-10-03 1991-07-10 Bayer Ag Elasthan fibres with high elasticity and tenacity and process for their preparation
US5061426A (en) * 1989-10-03 1991-10-29 Bayer Aktiengesellschaft Process for producing elastane fibers of high elasticity and strength
EP0684270A2 (en) * 1994-05-23 1995-11-29 Mitsubishi Gas Chemical Company, Inc. Aliphatic polyester carbonate and process for producing the same
EP0684270A3 (en) * 1994-05-23 1996-03-20 Mitsubishi Gas Chemical Co Aliphatic polyester carbonate and process for producing the same.
US5654380A (en) * 1994-05-23 1997-08-05 Mitsubishi Gas Chemical Company, Inc. Aliphatic polyester carbonate and process for producing the same

Also Published As

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EP0000510B1 (en) 1980-09-03
DE2860136D1 (en) 1980-12-11
JPS5422494A (en) 1979-02-20
JPS6256173B2 (en) 1987-11-24
IT1106853B (en) 1985-11-18
DE2732718A1 (en) 1979-02-15
US4192940A (en) 1980-03-11
IT7850345A0 (en) 1978-07-18

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