EP0000060B1 - Process for the preparation of bis-carbonates from diphenols and polyoxyalkylene glycols lengthened by carbonate groups and their application in the preparation of macromolecular thermoplastic polycarbonate polyether block copolymers. - Google Patents

Description

DE-A 2 650 533 claims a process for the clarification of carbonic acid aryl esters of polyalkylene oxide diols made from polyalkylene oxide diols with Mn over 135, preferably over 800, and carbonate group-elongated carbonic acid-bisaryl esters, which is characterized in that polyalkylene oxide diols with molecular weights Mn over 135, at temperatures between 100 ° C and 200 ° C in a vacuum below 35 torr together with carbonic acid bis-aryl esters in the presence of catalysts, with less than one mole of carbonic acid bis-aryl ester being used per OH group, and the hydroxylaryl compound formed being distilled off becomes.

worin

• R' und R" unabhängig voneinander H oder C1-C4-Alkyl sind,
• a eine ganze Zahl von 1 bis 6 ist und
• b eine ganze Zahl von 3 bis 350, insbesondere von 3 bis 250, ist, geeignet.

Such polyalkylene oxide diols are in particular

wherein

• R 'and R "are independently H or C1-C4-alkyl,
• a is an integer from 1 to 6 and
• b is an integer from 3 to 350, in particular from 3 to 250, is suitable.

The present invention now relates to the use of the carbonic acid aryl esters obtainable according to DE-A 2 650 533 mentioned above for the preparation of polyalkylene oxide di-bis-diphenol carbonates extended by carbonate groups; Another object of the present invention are the polyalkylene oxide di-bis-diphenol carbonates obtained via carbonate groups-elongated and their use for the production of polyether polycarbonates. Another object of the present invention are the polyether polycarbonates obtained according to the invention with an improved phase separation between the soft segment and the hard segment, which leads to better performance properties of the corresponding polycarbonate elastomers.

The transesterification of the polyalkylene oxide di-bis-aryl carbonates obtainable according to DE-A 2 650 533, which are extended by carbonate groups, with excess diphenols to the corresponding polyalkylene oxide di-bis-diphenol carbonates extended via carbonate groups takes place surprisingly smoothly without side reactions even at reaction temperatures up to 200 ° C. Neither does the molecular distribution given by the starting products change, nor does polyalkylene oxide diol regress, nor does polycondensation to polycarbonates.

The process according to the invention is characterized in that polyalkylene oxide diol bis-aryl carbonates which are extended by carbonate groups and are obtainable according to DE-A 2 650 533 by polyalkylene oxide diols with molecular weights Mn (number average) above 135, preferably above 800, with carbonic acid bis-aryl esters at temperatures between 100 ° C and 200 ° C, preferably between 110 ° C and 180 ° C, in a vacuum below 35 torr, preferably between 25 torr and 0.1 torr, in the presence of catalysts, where less than one mole of carbonic acid bis-aryl ester is used per OH group of the polyalkylene oxide diol, and the resulting hydroxyaryl compound is distilled off, with diphenols at temperatures between 100 ° C. and 200 ° C., preferably between 110 ° C. and 180 ° C. in a vacuum below 35 torr, preferably between 25 torr and 0.1 torr, heated in the presence of catalysts, being for a carbonic acid aryl ester group of the polyalkyleneoxy extended by carbonate groups ddiol-bis-aryl carbonates, more than 1 mol of diphenol, preferably between 1.1 mol and 2 mol of diphenol, are used, and the resulting hydroxyaryl compound is distilled off.

The present invention thus relates to polyalkylene oxide di-bis-diphenol carbonates which are extended by carbonate groups and obtained by this process according to the invention.

worin

• Ar ein substituierter oder unsubstituierter Arylrest mit 6 bis 18 C-Atomen, vorzugsweise Phenyl ist, erhältlichen Polyalkylenoxiddiol-bis-arylcarbonate der Formel 111
  
  worin n eine ganze Zahl von 2 bis 20, vorzugsweise 2 bis 10, bedeutet,
• Ar, R', R", a und b die für die Formel und II genannte Bedeutung haben, mit den Diphenolen der folgenden Formel IV
  
  worin
  
  0, S oder SO₂ bedeuten, und
• Y₁ bis Y₄ gleich oder verschieden sind und Wasserstoff oder Halogen, wie beispielsweise Chlor oder Brom, bedeuten, zu den über Carbonat-Gruppen-verlängerten Polyalkylenoxiddiol-bis-diphenol-carbonaten der Formel V umgesetzt
  
  worin n,
• R', R", a, b, X und Y1 die für die Formeln 111 und IV genannte Bedeutung haben.

In particular, those according to DE-A 2 650 533 from the polyalkylene oxide diols of the formula I with carbonic acid bis-aryl esters of the formula II

wherein

• Ar is a substituted or unsubstituted aryl radical having 6 to 18 carbon atoms, preferably phenyl, available polyalkylene oxide di-bis-aryl carbonates of the formula 111
  
  where n is an integer from 2 to 20, preferably 2 to 10,
• Ar, R ', R ", a and b have the meaning given for the formula and II, with the diphenols of the following formula IV
  
  wherein
  
  0, S or SO ₂ mean, and
• Y ₁ to Y _{4 are the} same or different and are hydrogen or halogen, such as chlorine or bromine, converted to the polyalkylene oxide di-bis-diphenol carbonates of the formula V which are extended by carbonate groups
  
  where n,
• R ', R ", a, b, X and Y1 have the meaning given for the formulas 111 and IV.

Suitable catalysts for the preparation according to the invention of the polyalkylene oxide di-bis-diphenol carbonates extended via carbonate groups are basic transesterification catalysts such as alkali metal or alkaline earth metal phenolates, alkali metal or alkaline earth metal alcoholates, tertiary amines such as triethylenediamine, morpholine, pyrrolidine, triethylamine and pyridine or metal compounds such as antimony trioxide, zinc chloride, titanium tetrachloride and titanium tetrabutyl ester.

The catalyst is used in amounts between 10 ppm and 200 ppm, based on the total weight of the polyalkylene oxide di-bis-aryl carbonate which is extended via carbonate groups and the diphenol used in each case.

These amounts of catalyst can be fallen below if necessary if the starting products do not contain any basic impurities when using the acidic catalysts and if they do not contain any acidic impurities when using the basic catalysts. In the interest of the lowest possible intrinsic color of the products according to the invention, the smallest possible amounts of catalyst are preferred.

The process according to the invention for the preparation of the polyalkylene oxide di-bis-diphenol carbonates extended via carbonate groups is preferably carried out in the absence of solvents for the reactants, in particular in bulk. If appropriate, solvents which are inert under the reaction conditions, such as, for example, aliphatic hydrocarbons, aromatic hydrocarbons which may be unsubstituted or substituted, for example, by nitro groups, can be used.

The reaction time for the transesterification process for the preparation of the polyalkylene oxide di-bis-diphenol carbonates extended via carbonate groups is between 1/2 and 24 hours, depending on the reaction temperature and the type and amount of the catalyst.

The polyalkylene oxide di-bis-diphenol carbonates extended by carbonate groups are prepared, for example, by obtaining a mixture of polyalkylene oxide di-bis-phenyl carbonate extended by carbonate groups in accordance with German patent application P 2 650 533.9 ( Le A 17 516) a diphenol and catalyst are heated in a vacuum to temperatures between 100 ° C. and 200 ° C., preferably between 110 ° C. and 180 ° C., and the phenol formed as the reaction progresses is distilled off from the reactor. The diphenol is used in excess, with more than 1 mol of diphenol, preferably between 1.1 mol and 2 mol of diphenol, being used per carbonic acid phenyl ester group of the polyalkylene oxide di-bis-phenyl carbonate. According to a particularly preferred embodiment, the disodium phenolate of bisphe nols A as catalyst, the reaction of a polyalkylene oxide di-bis-phenyl carbonate extended by carbonate groups, obtained according to DE-A 2 650 533, and bisphenol A in a molar ratio of bis-phenyl carbonate to bisphenol A of 1: 3 at 150 ° C. implemented in a vacuum between 25 and 0.1 torr.

The polyalkylene oxide di-bis-diphenol carbonates which are lengthened via carbonate groups and which are lengthened via carbonate groups and which are lengthened polyalkylene oxide di-bis-aryl carbonates which are lengthened by carbonate groups are prepared in accordance with DE-A 2 650 533.

• Hydrochinon
• Resorcin
• Dihydroxydiphenyle
• Bis-(hydroxyphenyl)-alkane
• Bis-(hydroxyphenyl)-cycloalkane
• Bis-(hydroxyphenyl)-sulfide
• Bis-(hydroxyphenyl)-äther
• Bis-(hydroxyphenyl)-ketone
• Bis-(hydroxyphenyl)-sulfone
• a,a-Bis-(hydroxyphenyl)-diisopropylbenzole
• sowie deren kernalkylierte und kernhalogenierte Verbindungen. Diese und weitere geeignete aromatische Dihydroxyverbindungen sind z.B. in den US-Patentschriften 3 028 365, 2 999 835, 3 148 172, 3271 368, 2991 273, 3 271 367, 3 280 078, 3 014 891 und 2 999 846 und in die deutschen Offenlegungsschriften 2 063 050, 2 211 957 aufgeführt.

Diphenol suitable for the preparation according to the invention of the polyalkylene oxide di-bis-diphenol carbonates which are extended via carbonate groups are:

• Hydroquinone
• Resorcinol
• Dihydroxydiphenyls
• Bis (hydroxyphenyl) alkanes
• Bis (hydroxyphenyl) cycloalkanes
• Bis (hydroxyphenyl) sulfides
• Bis (hydroxyphenyl) ether
• Bis (hydroxyphenyl) ketones
• Bis (hydroxyphenyl) sulfones
• a, a-bis (hydroxyphenyl) diisopropylbenzenes
• and their nuclear alkylated and nuclear halogenated compounds. These and other suitable aromatic dihydroxy compounds are described, for example, in US Pat. Nos. 3,028,365, 2,999,835, 3,148,172, 3,271,368, 2,991,273, 3,271,367, 3,280,078, 3,014,891 and 2,999,846 and in German Laid-open publications 2 063 050, 2 211 957.

• Bis-(4-hydroxyphenyl)-methan
• 4,4'-Dihydroxydiphenyl
• 2,4-Bis-(4-hydroxyphenyl)-2-methylbutan
• a,a-Bis-(4-hydroxyphenyl)-p-diisopropylbenzol
• 2,2-Bis-(3,5-dimethyl-4-hydroxyphenyl)-propan.

Suitable diphenols are, for example

• Bis (4-hydroxyphenyl) methane
• 4,4'-dihydroxydiphenyl
• 2,4-bis (4-hydroxyphenyl) -2-methylbutane
• a, a-bis (4-hydroxyphenyl) -p-diisopropylbenzene
• 2,2-bis (3,5-dimethyl-4-hydroxyphenyl) propane.

• 2,2-Bis-(4-hydroxyphenyl)-propan
• 1,1-Bis-(4-hydroxyphenyl)-cyclohexan
• 2,2-Bis-(3,5-dichlor-4-hydroxyphenyl)-propan und
• 2,2-Bis-(3,5-dibrom-4-hydroxyphenyl)-propan.

Preferred diphenols are, for example

• 2,2-bis (4-hydroxyphenyl) propane
• 1,1-bis (4-hydroxyphenyl) cyclohexane
• 2,2-bis (3,5-dichloro-4-hydroxyphenyl) propane and
• 2,2-bis (3,5-dibromo-4-hydroxyphenyl) propane.

The diphenols suitable according to the invention can be used both alone and in groups.

Polyalkylene oxide di-bis-diphenol carbonates extended by carbonate groups according to the invention are thus, for example, those of the formulas Va-Vh:

R ', R ", n, a and b have the meanings given for the formulas I and 111 in the formulas Va to Vh.

The polyalkylene oxide di-bis-diphenol carbonates extended by carbonate groups according to the invention can be used as starting bisphenols in the production of polycarbonates by the known two-phase interfacial polycondensation process. This gives polyether polycarbonates of a certain structure.

The process according to the invention for the preparation of these polyether polycarbonates is characterized in that the polyalkylene oxide di-bis-diphenol carbonates according to the invention which are extended via carbonate groups, in particular those of the formula V, with other diphenols, in particular with those of the formula IV, and with Reacts phosgene according to the two-phase interfacial polycondensation process known for polycarbonate production at pH values between 9 and 14 temperatures between 0 ° C. and 80 ° C., preferably between 15 ° C. and 40 ° C. The polyether polycarbonates obtained according to the invention are characterized by the presence of an amorphous (soft) polyether phase and a crystalline (hard) polycarbonate phase or an amorphous-crystalline (hard) polycarbonate phase.

Morphologically speaking, the polyether polycarbonates have two different, spatially separated phases, i.e. Areas composed of a continuous amorphous polyether phase and a crystalline or amorphous-crystalline polycarbonate phase.

The high molecular weight, segmented, thermoplastically processable polyether polycarbonates, made from polyalkylene oxide di-bis-diphenol carbonates which are extended via carbonate groups, show additional advantages over other polyether polycarbonates, for example also those of German Offenlegungsschrift 2,636,784, e.g. an even better phase separation, which leads to better performance properties of the corresponding polyether polycarbonates.

Because of their multiphase nature, the polyether polycarbonates according to the invention have better heat resistance than comparable single-phase polyether polycarbonates.

Single-phase polyether polycarbonates are described, for example, in U.S. Patent 3,151,615. They can be obtained by various processes, but preferably by the "pyridine process" known from polycarbonate production.

The production of two-phase polymers, for example polycarbonate-polycaprolactones, has so far only been possible using bishloroformic acid esters of polycaprolactones and polycarbonate oligomers (see French patent specification 2,235,965).

The same applies to the polyether polycarbonates of DE-B 1 162 559, although they are not shown to be two-phase.

The use according to the invention of the polyalkylene oxide di-bis-diphenol carbonates extended by carbonate groups according to the invention has the advantage over the use of corresponding bischloroformic acid esters that they are insensitive to hydrolysis and thus have better storage stability and clearly bifunctional reactivity.

The polyether polycarbonates according to the invention have improved heat resistance, in particular because of their crystalline polycarbonate phase.

The different phases of the polyether polycarbonates according to the invention can be identified with the aid of differential thermal analysis, for example the polyether phase having a glass transition temperature <20 ° C, the amorphous fraction in the polycarbonate phase having a glass transition temperature between 100 ° C and 150 ° C and the crystalline fraction Polycarbonate phase has a crystallite melting point between 170 ° C and 250 ° C.

The high molecular weight, segmented, thermoplastically processable polyether polycarbonates, produced by the process according to the invention, show not only the special thermal resistance, but also good transparency, highly elastic behavior and excellent tear resistance of _> 400%.

• 4,4'-Dihydroxy-diphenyl
• Bis-(4-hydroxyphenyl)-methan
• 2,4-Bis-(4-hydroxyphenyl)-2-methylbutan
• a,a-Bis-(4-hydroxyphenyl)-p-diisopropylbenzol
• 2,2-Bis-(3-chlor-4-hydroxyphenyl)-propan
• Bis-(hydroxyphenyl)-sulfid und
• 2,2-Bis-(3,5-dimethyl-4-hydroxyphenyl)-propan.

The other diphenols suitable for the production according to the invention of the polyether polycarbonates from the polyalkylene oxide di-bis-diphenol carbonates extended by carbonate groups according to the invention are already those for the production of the carbonate group extended polyalkylene oxide di-bis-diphenol carbonates mentioned, in particular those of the formula IV of this patent application; are suitable, for example

• 4,4'-dihydroxy-diphenyl
• Bis (4-hydroxyphenyl) methane
• 2,4-bis (4-hydroxyphenyl) -2-methylbutane
• a, a-bis (4-hydroxyphenyl) -p-diisopropylbenzene
• 2,2-bis (3-chloro-4-hydroxyphenyl) propane
• Bis (hydroxyphenyl) sulfide and
• 2,2-bis (3,5-dimethyl-4-hydroxyphenyl) propane.

2,2-Bis- (4-hydroxyphenyl) propane, 2,2-bis (3,5-dichloro-4-hydroxyphenyl) propane, 2,2 are preferred as other diphenols for the production of the polyether polycarbonates according to the invention -Bis (3,5-dibromo-4-hydroxyphenyl) propane and 1,1-bis (4-hydroxyphenyl) cyclohexane are used. Any mixtures of these other diphenols can also be used.

By incorporating small amounts of trifunctional or more than trifunctional compounds, in particular those with three or more than three phenolic hydroxyl groups, preferably between 0), 05-2 mol.% (Based on the diphenols used), branched products are obtained better flow behavior during processing.

• Phloroglucin, 4,6 - Dimethyl - 2,4,6 - tri - (3 - hydroxyphenyl) - hepten - 2, 4,6 - Dimethyl - 2,4,6 - tri(4 - hydroxyphenyl) - heptan, 1,3,5 - Tri(4 - hydroxyphenyl) - benzol, 1,1,1 - Tri - (3 - hydroxyphenyl) - äthan, Tri - (4 - hydroxyphenyl) - phenylmethan, 2,2 - Bis - [4,4 - (4,4' - dihydroxyphenyl)cyclohexyl] - propan, 2,4, - Bis - (4 - hydroxyphenyl - isopropyl) - phenol, 2,6 - Bis - (2' - hydroxy - 5' - methyl - benzyl) - 4 - methyl - phenol, 2,4 - Dihydroxybenzoesäure, 2 - (4 - Hydroxyphenyl) - 2 - (2,4 - dihydroxyphenyl) - propan und 1,4 - Bis - (4',4" - dihydroxytriphenyl - methyl) - benzol und 3,3 - Bis - (4 - hydroxyphenyl) - 2 - oxo - 2,3 - dihydroindol sowie 3,3 - Bis - (3 - methyl - 4 - hydroxyphenyl) - 2 - oxo - 2,3 - dihydroindol.

As a trifunctional or more than trifunctional connection, two suitable types are:

• Phloroglucin, 4,6-dimethyl-2,4,6-tri - (3-hydroxyphenyl) -hepten-2, 4,6-dimethyl-2,4,6-tri (4-hydroxyphenyl) -heptane, 1,3 , 5 - Tri (4 - hydroxyphenyl) benzene, 1,1,1 - Tri - (3 - hydroxyphenyl) ethane, Tri - (4 - hydroxyphenyl) phenylmethane, 2,2 - bis - [4,4 - ( 4,4 '- dihydroxyphenyl) cyclohexyl] - propane, 2,4, - bis - (4 - hydroxyphenyl - isopropyl) - phenol, 2,6 - bis - (2' - hydroxy - 5 '- methyl - benzyl) - 4 - methyl - phenol, 2,4 - dihydroxybenzoic acid, 2 - (4 - hydroxyphenyl) - 2 - (2,4 - dihydroxyphenyl) propane and 1,4 - bis - (4 ', 4 "- dihydroxytriphenyl - methyl) - benzene and 3,3 - bis - (4 - hydroxyphenyl) - 2 - oxo - 2,3 - dihydroindole and 3,3 - bis - (3 - methyl - 4 - hydroxyphenyl) - 2 - oxo - 2,3 - dihydroindole.

The polyether polycarbonates according to the invention can also be branched via the polyether component, in that the aryl esters of carbonic acid aryl esters of polyether polyols having three or four aryl groups, which are extended by carbonate groups and extended according to DE-A 2 650 533, can be branched with the di-, Tri- and / or tetraphenols to corresponding polyether polyol polyphenol carbonates according to the process of the present invention, and the resulting polyphenols in molar amounts up to 50 mol%, based on moles of polyether diol bis-diphenol carbonates used the polyether-polycarbonate synthesis used in accordance with the present invention.

The chain length of the polyether polycarbonates can be increased by adding a chain terminator, e.g. a monofunctional phenol such as phenol, 2,6-dimethylphenol, p-bromophenol or p-tert-butylphenol can be set, it being possible to use between 0.1 and 10 mol% of chain terminator per mole of diphenol used.

If necessary, the chain length of the polyether polycarbonates can be adjusted, for example, by adding polyether monool monodiphenol carbonates in molar amounts, based on moles of carbonate group-extended polyether diol bis-diphenol carbonates, to up to about 50 mol%.

The high-molecular, segmented, thermoplastically processable polyether polycarbonates are produced according to the invention by the two-phase interface polycondensation process. For this purpose, one of the aforementioned other diphenols or mixtures of the aforementioned other diphenols are dissolved in an alkaline aqueous solution. Likewise, the polyakylene oxide di-bis-diphenyol carbonates extended by carbonate groups according to the invention, in particular those of formula V, or their mixtures are dissolved and added in an inert organic solvent which is not miscible with water. Then at a temperature between 0 ° C and 80 ° C, preferably between 15 ° C and 40 ° C and a pH between 9 and 14 phosgene. After phosgenation, the polycondensation is carried out by adding 0.2-10 mol% of tertiary aliphatic amine, based on mol of diphenol. Times between 5 minutes and 90 minutes are required for phosgenation and times between 3 minutes and 3 hours for polycondensation.

The present invention thus relates to the preparation of polyether polycarbonates, which is characterized in that the polyalkylene oxide di-bis-diphenol carbonates, in particular those of the formula V, which are extended via carbonate groups, with other diphenols, in particular those of the formula IV, and with phosgene in a liquid mixture of inert organic solvent and alkaline aqueous solution at temperatures between 0 ° C and 80 ° C, preferably between 15 ° C and 40 ° C, at a pH between 9 and 14, and after the phosgene is polycondensed by adding 0.2 mol% to 10 mol% of tertiary aliphatic amine, based on the molar amount of diphenol, the weight ratio of polyalkylene oxide diol bis-diphenol carbonate extended to carbonate groups to other diphenol of the polycarbonate content and the polyether content of the polyether polycarbonates is determined.

The present invention thus relates to polyether polycarbonates obtained by this process according to the invention.

• a) isoliert nach bekannten Verfahren, beispielsweise durch Ausfällen mit Methanol oder Äthanol, und anschliessend getrocknet und getempert, oder Scherkräften unterworfen oder in organischen Lösungsmitteln gelöst und gelieren lassen oder
• b) bei der Isolierung beispielsweise im Ausdampfextruder bereits Scherkräften unterworfen, oder
• c) vor der Isolierung in dem bei der Herstellung der Polyäther-Polycarbonate nach dem Zweiphasengrenzflächenverfahren verwendeten Lösungsmittel gelieren lassen.

The solutions of the polyether polycarbonates obtained in the organic solvents are worked up analogously to the solutions of the thermoplastic polycarbonates produced by the two-phase interfacial process, the polyether polycarbonates also being post-treated, namely that they become either.

• a) isolated by known methods, for example by precipitation with methanol or ethanol, and then dried and tempered, or subjected to shear forces or dissolved and gelled in organic solvents or
• b) already subjected to shear forces during isolation, for example in the evaporation extruder, or
• c) gel before isolation in the solvent used in the manufacture of the polyether polycarbonates by the two-phase interfacial process.

Suitable inert organic solvents for the production process of the polyether polycarbonates according to the invention are water-immiscible aliphatic chlorinated hydrocarbons such as methylene chloride, chloroform and 1,2-dichloroethene, or chlorinated aromatics such as chlorobenzene, dichlorobenzene and chlorotoluene or mixtures of these solvents.

Solutions of Li OH, NaOH, KOH, Ca (OH) ₂ and / or Ba (OH) ₂ in water are suitable as alkaline aqueous solutions for the process according to the invention.

Suitable tertiary aliphatic amines for the process according to the invention are those having 3 to 15 carbon atoms, for example trimethylamine, triethylamine, n-tripropylamine and n-tributylamine and, depending on the diphenol used, vary between 0.2-5 mol% when used of tetramethyl-substituted diphenols between 5-10 mol%, based in each case on the total molar amount of diphenols used (= respective sum of polyalkylene oxide di-bis-diphenol carbonates and other diphenols extended by carbonate groups).

• a. Durch Abdestillieren des organischen Lösungsmittel bis zu einer bestimmten Konzentration, wobei; eine hochprozentige (etwa 30-40 Gew.-%) Polymerlösung erhalten wird, beim anschliessenden langsamen Verdampfen des restlichen Lösungsmittels geliert das Polyäther-Polycarbonat.
• b. Durch Fällen der Polyäther-Polycarbonate aus der organischen Phase mit organischen Lösungsmitteln, wobei zum Ausfällen sich beispielsweise Methanol, Äthanol, Isopropanol, Aceton, aliphatische Kohlenwasserstoffe und cycloaliphatische Kohlenwasserstoffe eignen.
• c. Durch Isolierung der Polyäther-Polycarbonate im Ausdampfextruder, bei Temperaturen von etwa 160-240°C unter den für die Polycarbonatextrusion bekannten Bedingungen und unter Anwendung von Scherkräften.

The polyether polycarbonates produced by the process according to the invention can be isolated by the following processes:

• a. By distilling off the organic solvent to a certain concentration, whereby; a high-percentage (about 30-40 wt .-%) polymer solution is obtained, the subsequent slow evaporation of the remaining solvent gels the polyether polycarbonate.
• b. By precipitation of the polyether polycarbonates from the organic phase with organic solvents, methanol, ethanol, isopropanol, acetone, aliphatic hydrocarbons and cycloaliphatic hydrocarbons being suitable for the precipitation.
• c. By isolating the polyether polycarbonates in the evaporation extruder, at temperatures of about 160-240 ° C. under the conditions known for polycarbonate extrusion and using shear forces.

The gelation of the polyether polycarbonates produced by the process according to the invention, .seis it without isolation in the processed organic phase of the two-phase reaction mixture or in a separate solution of the previously isolated polyether polycarbonates in organic solvents, is carried out by cooling the high-percentage polymer solution, whereby for the gelation each Depending on the amount of polyether or polycarbonate, times between 5 minutes and 12 hours at temperatures between 0 ° C and 40 ° C are required.

The gelled product can be worked up to a powder grain mixture, the polyether polycarbonate obtained being dried in vacuo for 48 hours at 50 ° C. and for 24 hours at 100 ° C.

Organic solvents such as methylene chloride, benzene, toluene or xylene are suitable as solvents for the separate gelation of the isolated polyether polycarbonates.

The insulated polyether polycarbonates are tempered between 5 minutes and 24 hours at temperatures between 40 ° C and 170 ° C.

The action of shear forces on the isolated polyether polycarbonates takes place between 0.5 and 30 minutes, at temperatures between 130 and 240 ° C and under shear forces between 0.2 and 0.7 KWh per kg polymer. The amount of phosgene depends on the diphenol used, the stirring action and the reaction temperature, which can be between about 0 ° C. and about 80 ° C., and is generally 1.1-3.0 mol of phosgene per mol of diphenol.

The reaction according to the invention of the polyalkylene oxide di-bis-diphenol carbonates according to the invention extended via carbonate groups with diphenols and with phosgene is carried out quantitatively; the respective reactant ratio of polyalkylene oxide di-bis-diphenol carbonate extended via carbonate groups to other diphenol is thus determined from the polycarbonate fraction and the polyether fraction to be synthesized in each case polyether polycarbonates.

The proportion of polycarbonate in the polyether polycarbonates produced by the process according to the invention is, depending on the desired property profile, approximately between 30 and 95, preferably approximately between 35 and 80% by weight, the hardness and heat resistance increasing with increasing polycarbonate content, and the elasticity and elongation at break decreases.

worin D für die Diphenolat-Reste im Polyäther-Polycarbonat steht, insbesondere an aromatischen Polycarbonatstruktureinheiten der Formel IVa zu verstehen

worin X und Y, bis Y₄ die für Formel IV genannte Bedeutung haben.The polycarbonate content of the polyether polycarbonates according to the invention is the amount by weight of aromatic polycarbonate structural units of the following formula VI

where D stands for the diphenolate residues in the polyether polycarbonate, in particular to understand aromatic polycarbonate structural units of the formula IVa

wherein X and Y to Y _{4 have} the meaning given for formula IV.

worin R', R", a, b die für die Formel 1 gennante Bedeutung haben und n eine ganze Zahl von 2 bis 20, vorzugsweise 2-10, bedeutet.The polyether fraction of the polyether polycarbonates according to the invention is therefore to be understood as the amount by weight of polyalkylene oxide diolate block units which are extended by carbonate groups, in particular those of the formula VII,

wherein R ', R ", a, b have the meaning given for formula 1 and n is an integer from 2 to 20, preferably 2-10.

The present invention thus also relates to polyether polycarbonates which are characterized in that they contain about 30 to 95% by weight, preferably about 35 to 80% by weight, of aromatic polycarbonate structural units of the formula VI, in particular those of the formula IVa, and approximately 70 to 5% by weight, preferably approximately 65 to 20% by weight, of polyalkylene oxide diolate block units which are extended by carbonate groups, in particular those of the formula VII.

worin

• Y H, Cl, Br oder CH₃ ist, und aus 70 bis 5 Gew.-%, vorzugsweise 65 bis 20 Gew.-% an über Carbonat-Gruppen-verlängerten Polyalkylenoxiddiolat-Blockeinheiten der Formel VII bestehen.

Polyether polycarbonates according to the invention are, for example, those which consist of 30 to 95% by weight, preferably 35 to 80% by weight, of polycarbonate structural units of the formula IVb

wherein

• Y is H, Cl, Br or CH ₃ , and consist of 70 to 5% by weight, preferably 65 to 20% by weight, of polyalkylene oxide diolate block units of the formula VII which are extended by carbonate groups.

The polyether polycarbonates according to the invention should have average molecular weights Nlw (weight average) of 25,000 to 250,000, preferably from 40,000 to 150,000, determined by the light scattering method using the scattered light photometer. The relative solution viscosities q rel. (measured on 0.5 g in 100 ml CH ₂ Cl ₂ at 25 ° C.) of the polyether polycarbonates according to the invention are between 1.3 and 3.0, preferably between 1.4 and 2.6.

The high molecular weight, segmented, thermoplastically processable polyether polycarbonates produced by the process according to the invention are characterized in that, measured by means of differential thermal analysis, the polyether content is amorphous and a freezing temperature between -100 ° C. and + 100 ° C., preferably between -80 ° C. and + 20 ° C, and that the polycarbonate portion is partially crystalline with a crystallite melting temperature of the crystalline polycarbonate portion of at least 160 ° C, preferably between 165 ° C and 250 ° C, and that the glass transition temperature of the amorphous polycarbonate portion is over 80 ° C, preferably over 100 ° C.

This differentiation of the freezing temperature of the polyether portion from the freezing temperature and the crystallite melting temperature of the polycarbonate portion is characteristic of the phase separation of the polyether and polycarbonate portion.

The partial crystallinity, which can be demonstrated by a measurable enthalpy of fusion of the crystalline polycarbonate portion of the polyether polycarbonates according to the invention, which is at least 1-8 cal / g polymer, can be achieved by stretching and by the subsequent post-annealing (5 minutes to 24 hours) at 40-170 ° C or by the aforementioned action of shear forces during the thermoplastic Processing in a multi-screw extruder can be increased by 50%, whereby the heat resistance of the products increases, the appearance changes from transparent to opaque to opaque.

The partially crystalline elastic polyether polycarbonates can in each case below or in the region of the crystallite melting point of the crystalline polycarbonate component at temperatures from 130 ° C. to max. 250 ° C are processed thermoplastic, whereby a substantial proportion of the crystallinity is not lost. At processing temperatures above the crystalline melting point of the crystalline polycarbonate content, amorphous, transparent products are obtained.

The crystalline fraction of the polycarbonate fraction of the polyether polycarbonates according to the invention can thus be varied, the enthalpy of fusion of the crystalline polycarbonate fraction, in order to have good heat resistance of the polyether polycarbonates in practice, at about 1-8 cal / g polymer, preferably at 2, 5-5.5 cal / g polymer is.

If the inventive processing and isolation of the polyether polycarbonates is carried out without tempering, without gelling and without the action of shear forces, then single-phase polyether polycarbonates are obtained, that is to say products with only a freezing temperature which can be measured by means of differential thermal analysis.

The UV stability and hydrolysis stability of the polyether polycarbonates according to the invention can be improved by the amounts of UV stabilizing agents which are customary for thermoplastic polycarbonates, such as, for example, substituted "benzophenones" or "benzotriazoles", by hydrolysis protective agents, such as, for example, mono- and especially polycarbodumides (cf. W. Neumann, J. Peter, H, Holtschmidt and W. Kallert, Proceeding of the 4th Rubber Technology Conference London, May 22-25, 1962, pp. 738-751) in amounts of 0.2-5% by weight. %, based on the weight of the polyether polycarbonates, and by anti-aging agents known in the chemistry of thermoplastic polyethers and thermoplastic polycarbonates.

To modify the products according to the invention, substances such as carbon black, kieselguhr, kaolin, clays, CaF ₂ , CaC0 ₃ , aluminum oxides and conventional glass fibers in amounts of 2 to 40% by weight, based in each case on the total weight of the molding composition and inorganic pigments, can be used both as Fillers as well as nucleating agents are added.

If flame-retardant products are desired, about 5 to 15% by weight, based on the weight of the polyether polycarbonates, of flame retardants known in the chemistry of thermoplastic polyethers and thermoplastic polycarbonates, such as e.g. Antimony trioxide, tetrabromophthalic anhydride, hexabromocyclododecane, tetrachloro- or tetrabromobisphenol-A or tris (2,3-dichloropropyl) phosphate are admixed, with statistically incorporated tetrachloro- and tetrabromobisphenols also showing flame retardant properties in the polycarbonate fractions of the polycarbonates according to the invention.

Furthermore, processing aids known in the chemistry of thermoplastic polyethers and thermoplastic polycarbonates, such as release aids, can be used effectively.

The polyether polycarbonates obtained by the process according to the invention can advantageously be used wherever a combination of hardness and elasticity, in particular low-temperature flexibility, is desired, e.g. in body construction, for the production of low-pressure tires for vehicles, for wrapping hoses, plates, pipes and for flexible drive pulleys.

The average molecular weights listed in the following examples are number average Mn and determined by determining the OH number.

angegeben.The Staudinger index [ _{1]] given} in example A was measured in THF at 25 ° C and in

specified.

• H. G. Elias: 'Makromoleküle', Hüthig & Wepf-Verlag, Basel, S. 265.

For the definition of the Staudinger index see:

• HG Elias: 'Macromolecules', Hüthig & Wepf-Verlag, Basel, p. 265.

The relative solution viscosity η _rel of Examples C ₁ -C ₆ is defined by the viscosity of 0.5 g of polyether polycarbonate in 100 ml of methylene chloride at 25 ° C.

The tensile strength and the elongation at break were measured according to DIN 53 455 and 53 457, respectively.

Gel chromatographic studies were carried out in tetrahydrofuran with styric acids (separation range 1.5 × 10 ⁵ A, 1 × 10 ⁵ A, 3 × 10 ⁴ A and 2 × 10 ³ A) at room temperature.

The calibration of bisphenol A polycarbonate was used for the determination. There are no major deviations compared to the Mw determination using the light scattering method.

The differential thermal analysis (DTA) was carried out with the device "DuPont, model 900". To interpret the freezing temperature, the approximate middle of the softening range was chosen according to the tangent method and the approximate center of the endothermic peak of the melting curve for the crystallite melting point.

Example A

1) 2000 parts by weight of polytetrahydrofuran diol with a molecular weight Mn of 2000 and with a GPC curve shown by curve (1) in FIG. 1, 321 parts by weight of diphenyl carbonate, 0.1 part by weight of sodium phenolate and 0.2 Parts by weight of 2,6-di-tert-butyl-p-cresol are stirred. Nitrogen and a vacuum of 6 Torr for 1.5 hours at 110 ° C, 2 hours at 130 ° C and 2 hours at 150 ° C; during this time, phenol is distilled off from the reaction mixture. If desired, residual traces of phenol can then be separated off at 190 ° C / 0.1 Torr in a thin-film evaporator. A colorless, viscous oil with a molecular weight Mn of 4200 and a Staudinger index [q] THF = 0.24 is obtained. The OH number is zero. The GPC curve of this product is shown as curve (2) in Fig. 1.

Example B1

Preparation of a polytetrahydrofuran diol bis (bisphenol A) carbonate which still contains 1% by weight bisphenol A.

2100 parts by weight of bisphenyl carbonate of a polytetrahydrofuran diol having an average molecular weight Mn = 4200 and extended by carbonate groups, which was prepared according to Example A, 251.1 parts by weight of 2,2-bis (4-hydroxyphenyl) propane (bisphenol A) and 0.3 part by weight of catalyst (sodium bisphenolate of bisphenol A to bisphenol A = 1: 100) are heated at 150 ° C. and 0.3 torr for 9 hours with stirring and under a nitrogen atmosphere. During this time, phenol is distilled off from the reaction mixture. The reaction product obtained is a clear, viscous 01.

Example B2

Preparation of a carbonate group-extended polytetrahydrofuran-diol bis (bisphenol A) carbonate which still contains 3.7% by weight bisphenol A.

320 parts by weight of bisphenyl carbonate of a polytetrahydrofuran diol having an average molecular weight Mn = 3200 and extended by carbonate groups, which was prepared according to Example A, 59.4 parts by weight of 2,2-bis. (4-hydroxyphenyl) propane (bisphenol A) and 0.01 part by weight of sodium phenolate are first heated at 125 ° C. for 1 hour, then at 150 ° C. and 0.5 torr while distilling off phenol, with stirring and under a nitrogen atmosphere. The reaction product obtained is a clear, viscous oil.

Example B3

Production of a carbonate group-extended polypropylene oxide diol bis (bisphenol A) carbonate which still contains 3% by weight bisphenol A.

315 parts by weight of bisphenyl carbonate of a polypropylene oxide diol having an average molecular weight Mn = 4200 and lengthened via carbonate groups and which was prepared according to Example A, 44.5 parts by weight of bisphenol A and 0.05 part by weight of catalyst (sodium bisphenolate of bisphenol A to bisphenol A = 1: 100) are heated with stirring and nitrogen atmosphere at 125 ° C for one hour, then at 150 ° C and 0.8 Torr for 5 hours. During this time, phenol is distilled off from the reaction mixture. The product obtained is a clear, viscous oil.

Example B4

Preparation of a carbonate group-extended polytetrahydrofuran-di-bis-diphenol carbonate of the formula Vf which still contains 3.6% by weight of 2,2-bis (3,5-dimethyl-4-hydroxyphenyl) propane.

315 parts by weight of bisphenyl carbonate of a polytetrahydrofuran diol having an average molecular weight Mn = 4200 and extended by carbonate groups, which was prepared according to Example A, 55.5 parts by weight of 2,2-bis (3,5-dimethyl-4-hydrophenyl) Propane and 0.25 part by weight of catalyst (sodium bisphenolate of bisphenol A: bisphenol A = 1: 100) are first stirred and under a nitrogen atmosphere at 125 ° C. for 1 hour, then at 150 ° C. and 0.1 Torr for 4 hours Distilling phenol heated. A clear, viscous oil is obtained.

Example B5

Preparation of a carbonate group-extended polypropylene oxide diol bis-diphenol carbonate of the formula Vf which still contains 2.5 parts by weight of 2,2-bis (3,5-dimethyl-4-hydroxyphenyl) propane.

310 parts by weight of bisphenyl carbonate of a polypropylene oxide diol having an average molecular weight Mn = 6200 and extended by carbonate groups and which was prepared according to Example A, 37 parts by weight of 2,2-bis (3,5-dimethyl-4-hydroxyphenyl) Propane and 0.02 part by weight of catalyst (sodium bisphenolate of bisphenol A: bisphenol A = 1: 100) are first stirred at 125 ° C. for 1 hour, then at 150 ° C. and 0.05 torr with distillation while stirring and under a nitrogen atmosphere heated by phenol. A clear, viscous oil is obtained.

Example C1

Production of the polyether polycarbonate with 50 wt .-% polyether.

2,264 parts by weight of this viscous oil from Example B1, dissolved in 30 liters of CH _Z CI _Z, are converted into a solution of 1545 parts by weight of 2,2-bis (4-hydroxyphenyl) propane (bisphenol A) and 47. 2 parts by weight p- tert-Butylphenol in 1400 parts by weight of 45 percent NaOH and 30 liters of distilled water.

1167 parts by weight of phosgene are introduced over the course of 40 minutes at 20-25 ° C. with stirring and under a nitrogen atmosphere. During the introduction, 1730 parts by weight of 45% NaOH are simultaneously added dropwise in such a way that the pH remains constant at pH 13. After introducing phosgene, 7.9 parts by weight of triethylamine are added and the mixture is stirred for 1 hour. The organic phase is separated off, washed successively with 2% phosphoric acid and finally with distilled water until the electrolyte is free. After the water has been separated off, the organic phase can be worked up by the following methods:

C. 1.1

By distilling off the CH ₂ C1 ₂ to a certain concentration or by adding chlorobenzene to the organic phase and distilling off all of the methylene chloride, a high-percentage (about 30-40% by weight) polymer solution is obtained. Subsequent slow evaporation of the remaining methylene chloride or chlorobenzene causes the polyether polycarbonate to gel and can be worked up to a powder-grain mixture. The polyether polycarbonate obtained is dried for 48 hours at 50 ° C. and 24 hours at 100 ° C.

C. 1.2

A finely divided solid product is obtained by distilling off the solvent, drying in a vacuum drying cabinet at about 80-110 ° C. and 15 torr and then grinding.

C. 1.3

By precipitation of the polyether polycarbonate from the organic phase with, for example, methanol, ethanol, acetone, aliphatic hydrocarbons and cycloaliphatic hydrocarbons and subsequent drying in a vacuum drying cabinet at 80-110 ° C. and 15 torr.

C. 1.4

By concentrating the organic phase in the evaporation extruder and subsequent extrusion at about 160-240 ° C under the conditions known for polycarbonate extrusion.

The rel. Viscosity of the polyether polycarbonate obtained according to C. 1.1 - C. 1.4 is η _rel = 1.52 (measured in CH _Z CI ₂ at 25 ° C and c = 5 g / I). According to gel chromatographic determination, the polyether polycarbonate shows a maximum at 40,000. It has 50% by weight of polyether and 50% by weight of polycarbonate. Some mechanical properties of a film cast from methylene chloride are: tear strength 45.9 (MPA) (measured according to DIN 53 455), elongation at break 483% (measured according to DIN 53 455).

According to differential thermal analysis, the granulated polyether polycarbonate shows a glass transition temperature of the polyether portion of -75 ° C, a glass transition temperature of the polycarbonate of 145 ° C and a crystallite melting point of the polycarbonate portion of approx. 215 ° C.

Example C2

Production of a polyether polycarbonate with 60 wt .-% polyether.

134.3 parts by weight of the viscous oil as example B1, dissolved in 1725 parts by weight of methylene chloride, are converted into a solution of 58.2 parts by weight of 2,2-bis (4-hydroxyphenyl) propane (bisphenol A) and 1.42 parts by weight . Parts of p-tert-butylphenol in 1300 parts by weight of dist. Water and 56 parts by weight of 45% sodium hydroxide solution. 85.6 parts by weight of phosgene are introduced with stirring in a nitrogen atmosphere over the course of 45 minutes, while 95 parts by weight of 45% sodium hydroxide solution are added dropwise at the same time in order to keep pH 13 constant. After introducing phosgene, 0.32 part by weight of triethylamine is added. The approach becomes more viscous. After 1 hour, the organic phase is separated off and the polyether polycarbonate is obtained as described in Example C1 (workup C _1.1 -C _1.4 ).

The rel. Viscosity of the polyether polycarbonate is η _rel = 1.62 (in CH2C12).

Example C3

Production of a polyether polycarbonate with 50 wt .-% polyether.

120.6 parts by weight of the viscous oil from Example B2, dissolved in 1725 parts by weight of methylene chloride, are converted into a solution of 70 parts by weight of 2,2-bis (4-hydroxyphenyl) propane (bisphenol A) and 1.77 parts by weight . Parts of p-tert-butylphenol in 1300 parts by weight of dist. Water and 70 parts by weight of 45% sodium hydroxide solution. 58.3 parts by weight of phosgene are introduced with stirring in a nitrogen atmosphere over the course of 45 minutes, while 135 parts by weight of 45% sodium hydroxide solution are added dropwise at the same time in order to keep pH 13 constant. After introducing phosgene, 0.4 parts by weight of triethylamine are added. The approach becomes more viscous. After 1 hour, the organic phase is separated off and the polyether polycarbonate is obtained as described in Example C1 (workup C _1.1 -C _1.4 ).

The rel. Viscosity of the polyether polycarbonate is η _rel = 1.54 (in CH ₂ CI ₂ ).

Example C4

Production of a polyether polycarbonate with 50 wt .-% polyether.

115.3 parts by weight of the viscous oil from Example B3, dissolved in 1725 parts by weight of methylene chloride, become a solution of 65 parts by weight of 2,2-bis (4-hydroxyphenyl) propane (bisphenol A) and 1300 parts by weight of dist. Water and 70 parts by weight of 45% sodium hydroxide solution. 58.3 parts by weight of phosgene are introduced with stirring in a nitrogen atmosphere over the course of 45 minutes, while 135 parts by weight of 45% sodium hydroxide solution are added dropwise to keep pH 13 constant. After introducing phosgene, 0.4 parts by weight of triethylamine are added. The approach becomes more viscous. After 1 hour, the organic phase is separated off and the polyether polycarbonate is obtained as described in Example C1 (workup C _1.1 ―C _1.4 ).

The rel. Viscosity of the polyether polycarbonate is η _rel = 2.05 (in CH ₂ CI ₂ ).

According to differtial thermal analysis, the granulated polyether polycarbonate shows a glass transition temperature of the polyether portion of -57 ° C, a glass transition temperature of the polycarbonate of 145 ° C and a crystallite melting point of the polycarbonate portion of approx. 195 ° C.

Example C5

Production of a polyether polycarbonate from 2,2-bis (3,5-dimethyl-4-hydroxyphenyl) propane with 50% by weight of polyether.

119 parts by weight of the viscous oil from Example B4 and 0.6 part by weight of tributylamine (= 1 mol% per mole of bisphenol units), dissolved in 1725 parts by weight of methylene chloride, are converted into a solution of 73.2 parts by weight. Parts of 2,2-bis (3,5-dimethyl-4-hydroxyphenyl) propane ir 57.3 parts by weight of 45% sodium hydroxide solution and 1300 parts by weight of dist. Given water. 95.6 parts by weight of phosgene are introduced over the course of 30 minutes with stirring and under a nitrogen atmosphere, while 235 parts by weight of 45% strength sodium hydroxide solution are added dropwise at the same time in order to keep pH 13 constant. After the phosgene has been introduced, 5.4 parts by weight of tributylamine (= 9 mol% per mol of bisphenol units) are added for complete condensation. The approach becomes more viscous. After 3 hours, the organic phase is separated off and the polyether polycarbonate is obtained as described in Example C1 (workup C 1.1).

The rel. Viscosity of the polyether polycarbonate is η _rel = 1.63 (in CH ₂ Cl _z ).

Example C6

Production of a polyether polycarbonate from 2,2-bis (3,5-dimethyl-4-hydroxyphenyl) propane with 50% by weight of polyether.

112.8 parts by weight of the viscous oil from Example B5 and 0.6 part by weight of tributylamine (= 1 mol% per mole of bisphenol units), dissolved in 1725 parts by weight of methylene chloride, are dissolved in a solution of 79.3 parts by weight . Parts of 2,2-bis (3,5-dimethyl-4-hydroxyphenyl) propane in 57.3 parts by weight of 45% sodium hydroxide solution and 1300 parts by weight of dist. Given water. 95.6 parts by weight of phosgene are introduced over the course of 30 minutes with stirring and under a nitrogen atmosphere, while 235 parts by weight of 45% strength sodium hydroxide solution are added dropwise to keep pH 13 constant. After the phosgene has been introduced, 5.4 parts by weight of tributylamine (= 9 mol% per mol of bisphenol units) are added for complete condensation. The approach becomes more viscous. After 3 hours, the organic phase is separated off and the polyether polycarbonate is obtained as described in Example C1 (workup C 1.1).

The rel. Viscosity of the polyether polycarbonate is η _rel = 1.66 (in CH2CI2) ..

Claims (11)

1. A process for the preparation of polyalkylene oxide-diol bis-diphenol carbonates, lengthened via carbonate groups, characterised in that polyalkylene oxide-diols having molecular weights Mn (number-average) of over 135 are heated with carbonic acid bis-aryl esters at temperatures between 100°C and 200°C in vacuo below 35 mm Hg in the presence of catalysts, less than 1 mol of carbonic acid bis aryl ester being employed per OH group of the polyalkylene oxide-diol and the resulting hydroxy-aryl compound is distilled off and the resulting polyalkylene oxide-diol bis-aryl carbonates are then heated with diphenols at temperatures between 100° and 200°C in vacuo below 35 mm Hg in the presence of catalysts, more than 1 mol of diphenol being employed for one carbonic acid aryl ester group of the polyalkylene oxide-diol bis-aryl carbonate lengthened via carbonate groups and the resulting hydroxy-aryl compound is distilled off.

2. Polyalkylene oxide-diol bis-diphenol carbonates, lengthened via carbonate groups, obtained according to the process of claim 1.

3. Polyalkylene oxide-diol bis-diphenol carbonates, lengthened via carbonate groups, of the formula V

wherein

R' and R" independently of one another are H or C₁ to C₄ alkyl,

n is an integer from 2 to 20, preferably 2-10,

a is an integer of from 1 to 6, and

b is an integer of from 3 to 350,

X is

0, S or S0₂, and

Y₁ and Y₄ are identical or different and denote hydrogen or halogen, obtained according to the process of claim 1.

4. Polyalkylene oxide-diol bis-diphenol carbonates, lengthened via carbonate groups, according to claim 3, of the formula Vf

wherein

R', R", n, a and b have the meaning given in claim 3.

5. Polyalkylene oxide-diol bis-diphenol carbonates, lengthened via carbonate groups, according to claim 3, of the formula Vg

wherein

R', R", n, a and b have the meaning given in claim 4.

6. Polyalkylene oxide-diol bis-diphenol carbonates, lengthened via carbonate groups, according to claim 3, of the formula Vh

wherein

R', R", n, a and b have the meaning given in claim 4.

7. The use of the polyalkylene oxide-diol bis-diphenol carbonates of claims 2 to 6 for the preparation of polyether/polycarbonates.

8. A process for the preparation of polyether/polycarbonates, characterised in that the polyalkylene oxide-diol bis-diphenol carbonates of claims 2 to 6 are reacted with other diphenols and with phosgene in a liquid mixture of an inert organic solvent and an alkaline aqueous solution, at temperatures between 0°C and 80°C at a pH value between 9 and 14, and after the addition of phosgene, polycondensation is carried out by adding from 0.2 mol % to 10 mol %, relative to the molar amount of diphenol, of a tertiary aliphatic amine, the weight ratio of polyalkylene oxide-diol bis-diphenol carbonate to the other diphenol being determined by the proportion of polycarbonate and the proportion of polyether of the polyether/polycarbonates.

9. A process according to claim 8, characterised in that as the other diphenols those of the formula IV

are reacted, wherein

X denotes

O, S or S0₂ and

Y₁ to Y₄ are identical or different and denote hydrogen or halogen.

10. Polyether/polycarbonates obtained according to claims 8 and 9.

11. Polyether/polycarbonates characterised in that they consist of about 30 to 95% by weight of aromatic polycarbonate structural units of the formula IVa

wherein

X and Y₁ to Y₄ have the meaning given in claim 9 and of about 70 to 5% by weight of polyalkylene oxide-diol block units, lengthened via carbonate groups, of the formula VII

wherein

R', R" independently of one another are H or C₁ to C₄ alkyl,

a is an integer from 1 to 6 and b is an integer from 3 to 350, and

n is an integer from 2 to 20, preferably 2 to 10.

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