DE2726417C2 - - Google Patents

Description

The German patent application P 27 12 435.2 claims a process for the production of carbonic acid aryl esters from polyester polyols extended by carbonate groups Polyester polyols with n about 250, preferably over 600, and carbonic acid bisaryl esters, the result is characterized in that polyester polyols with molecular weights n (number average) over 250, preferably at Temperatures between 100 ° C and 200 ° C in a vacuum below 46.6 mbar together with carbonic acid bis-aryl esters in the presence heated by catalysts, with less per OH group is used as one mole of carbonic acid bis-aryl ester, and the resulting hydroxylaryl compound is distilled off.

In particular, reaction products are polyester polyols of polyvalent, preferably divalent and optionally additionally trihydric, alcohols with polyvalent, preferably dibasic carboxylic acids.  

The present invention now relates to a Process for the preparation of carbonate-extended groups Polyesterdiol-bis-diphenol carbonates, the is characterized in that polyester polyols with Molecular weights n (number average) over 250, with Carbonic acid bis-aryl esters at temperatures between 100 ° C and 200 ° C in a vacuum below 46.6 mbar in the presence of alkali or alkaline earth phenolates in quantities from 20 ppm to 200 ppm, based on the total weight of the used Polyester diols and the carbonic acid bis-aryl ester used, heated, per OH group of the polyester polyol less than 1 mole of carbonic acid bis-aryl ester be used and the resulting Hydroxyaryl compound is distilled off, and the obtained polyester diol extended by carbonate groups bis-aryl carbonates with diphenols at temperatures between 100 ° C and 200 ° C in a vacuum below 46.6 mbar in the presence of alkali or alkaline earth phenates in amounts from 10 pm to 200 ppm to the total weight of each used Carbonate groups extended polyester diol bis-aryl carbonate and the diphenol used in each case, heated, being for a carbonic acid aryl ester group of the polyester diol extended via carbonate groups bis-aryl carbonate used more than 1 mole of diphenol and the resulting hydroxyaryl compound is distilled off.  

The method according to the invention can also be characterized in this way be that the obtained, extended over carbonate groups Polyester di-bis-aryl carbonates together with excess carbonic acid bis-aryl ester Implemented diphenols.

The present invention also relates to Carbonate group-extended polyester diol bis-diphenol carbonates, obtained by the method according to the invention.

The present invention relates in particular via carbonate group-extended polyester diol bis-diphenol carbonates of the formula (IV)

wherein
- (Polyester) - the divalent residue of the reaction product of one or more dibasic alcohols with one or more dibasic carbonate acids is to be understood,
n is an integer from 2 to 20, preferably 2 to 10,

Y₁ and Y₄ are the same or different and are hydrogen or halogen, obtained after method according to the invention.

The present invention also relates to a Process for the production of polyester-polycarbonates, which is characterized in that the inventive about carbonate group-extended polyester diol bis-diphenol carbonates with other diphenols, monofunctional phenols as chain terminators and with Phosgene in a liquid mixture of inert organic solvents and alkaline aqueous Solution at temperatures between 0 ° C and 80 ° C at one converts pH between 9 and 14, and after Phosgene addition by adding 0.2 mol% to 10 mol% of tertiary aliphatic amine, based on the molar amount on diphenol, polycondensed, the weight ratio of over carbonate group extended Polyesterdiol-bis-diphenol carbonate to other diphenol of the polycarbonate portion and the polyester portion of the Polyester-polycarbonate is determined.

The subject of the present invention is in particular also a method which is characterized in that as other diphenols those of the formula (III)  

be implemented in what

Y₁ to Y₄ are the same or different and are hydrogen or halogen.

The transesterification according to the German patent application P 27 12 435.2 available from carbonate group-extended Polyesterdiol-bis-aryl carbonates with excess diphenols to the corresponding over carbonate Group-extended polyester diol bis-diphenol carbonates is surprisingly smooth without any side reactions themselves at reaction temperatures up to 200 ° C. Neither does the change from molecular distribution given to the starting products, there is still regression of polyester polyols, still done Polycondensation to polycarbonates.

The method according to the invention is preferably characterized in that that polyester diol bis-aryl carbonates extended by carbonate groups, according to the German patent application P 27 12 435.2 are available in that to polyester diols with molecular weights n (number average) preferably over 600 with carbonic acid bis-aryl esters at temperatures above  preferably between 110 ° C and 180 ° C, in vacuo, preferably between 33.3 mbar and 1.33 mbar, in the presence of Catalysts heated, with each OH group of the polyester diol less than one mole of carbonic acid bis-aryl ester are used and the corresponding hydroxyaryl compound is distilled off with diphenols Temperatures preferably between 110 ° C and 180 ° C in Vacuum, preferably 33.3 mbar and 0.13 mbar, in the presence heated by catalysts, being for a carbonic acid aryl ester group the one extended over carbonate groups Polyester di-bis-aryl carbonate preferably between 1.1 moles and 2 moles of diphenol are used, and the resulting hydrodyaryl compound is distilled off.

The preferred areas may or may not all are observed at the same time.

In particular, according to the German patent application P 27 12 435.2 made of polyester diols and carbonic acid bis-aryl esters of the formula I.

wherein
Ar is a substituted or unsubstituted aryl radical having 6 to 18 carbon atoms, preferably phenyl, obtainable via carbonate group-extended polyesterdiol-bis-arylcarbonates of the simplified formula (II)

wherein
- (Polyester) - represents the divalent radical of a polyester diol, n is an integer from 2 to 20, preferably 2 to 10, and
Ar has the meaning given for the formula (I), with the diphenols of the following formula (III)

wherein

Y₁ to Y₄ are the same or different and are hydrogen or halogen, such as chlorine or Bromine mean to those over-carbonate-extended Polyesterdiol bis-diphenol carbonates the simplified formula (IV) implemented

wherein
- (Polyester) -, n , X and Y₁ have the meaning given for the formula (II) and (III).

The inventive method for producing the Carbonate group-extended polyester diol bis-diphenol carbonate is preferably carried out in the absence of solvents for the reactants, especially in bulk. Possibly can be inert under the reaction conditions Solvents such as aliphatic hydrocarbons, aromatic hydrocarbons that are unsubstituted or substituted for example by nitro groups can be used.

The reaction time for the transesterification process for production the polyesterdiol-bis-diphenol carbonates, which are extended via carbonate groups depends on of the reaction temperature and the type and amount of the catalyst between 1/2 and 24 hours.

The production of those extended over carbonate groups Polyesterdiol-bis-diphenol carbonates are used, for example by making a mixture of carbonate-extended groups Polyester diol bis-phenyl carbonate received according to German patent application P 27 12 435.2 a diphenol and catalyst in vacuo to temperatures between 100 ° C and 200 ° C, preferably between 110 ° C and 180 ° C, heated with the progressive Reaction formed phenol is distilled off from the reactor. Here, the diphenol is in excess used, the per carbonic acid phenyl group of Polyesterdiol-bis-phenylcarbonate more than one mole Diphenol can be used, preferably between 1.1 moles  and 2 moles of diphenol can be used. According to one particularly preferred embodiment is with the disodium phenolate of bisphenol A as a catalyst the reaction from a via polyester diol-bis-phenyl carbonate extended by carbonate groups, obtained according to P 27 12 435.2, and Bisphenol A in a molar ratio of bis-phenyl carbonate to bisphenol A of 1: 3, at 150 ° C, in a vacuum between 33.3 and 0.13 mbar implemented.

Those for the production according to the invention of those extended via carbonate groups Polyester diol bis-diphenol carbonates necessary over carbonate group-extended polyester diol bis-aryl carbonates are according to the German patent application P 27 12 435.2. From this patent application the following part is taken over:

Subject of the German patent application P 27 12 435.2 is a process for the preparation of bis-carbonic acid monoaryl esters from over -OCOO groups-extended Polyester diols with n over 250, preferably over 600, and carbonic acid bis-aryl esters, characterized in that that polyester diols with molecular weights n (number average) over 250, preferably over 600, 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 46.6 mbar, preferably between 33.3 and 1.33 mbar, in the presence heated by catalysts, with each OH group of the polyester diol less than one mole of carbonic acid bis-aryl ester is used and the resulting hydroxyaryl compounds be distilled off.

Another subject of P 27 12 435.2 are aryl bis-carbonic acid of polyester diols extended by -OCOO groups.

Polyester polyols preferred according to P 27 12 435.2 are polyester diols. Thus, the preferred item from P 27 12 435.2 a method for  Production of bisaryl carbonates of carbonate-extended groups Polyester diols as well as those extended by carbonate groups Polyester di-bis-aryl carbonates.

The hydroxyl-containing polyesters according to P 27 12 435.2 Invention are, for example, implementation products of polyvalent, preferably divalent and optionally additionally trivalent alcohols with polyvalent, preferably dihydric, carboxylic acids. Instead of the free polycarboxylic acids can also be the corresponding Polycarboxylic anhydrides or equivalent Polycarboxylic esters of lower alcohols or their Mixtures can be used to produce the polyester polyols. The polycarboxylic acids can be more aliphatic, cycloaliphatic, be aromatic and / or heterocyclic in nature and, if appropriate, e.g. B. by halogen atoms, substituted and / or be unsaturated. Examples include: Oxalic acid, malonic acid, succinic acid, adipic acid, suberic acid, Azelaic acid, sebacic acid, carbonic acid, phthalic acid, terephthalic acid, Isophthalic acid, trimellitic acid, phthalic anhydride, Tetrahydrophthalic anhydride, hexahydrophthalic anhydride, Tetrachlorophthalic anhydride, endomethylene tetrahydrophthalic anhydride, Glutaric anhydride, maleic acid, Maleic anhydride, fumaric acid, dimeric and trimeric fatty acids such as oleic acid, optionally in a mixture with monomeric fatty acids. As polyhydric alcohols, optionally in Mixture with each other, e.g. B. ethylene glycol, propylene glycol (1,2) and - (1,3), butylene glycol- (1,4) and - (2,3), hexanediol- (1,6), Octanediol (1.8), neopentyl glycol, cyclohexanedimethanol, (1,4-bis-hydroxymethyl-cyclohexane), 2-methyl-1,3-propanediol, Glycerin, trimethylolpropane, hexanetriol- (1,2,6), butanetriol- (1,2,4), Trimethylolethane, pentaerythritol, quinite, further Thioglycol, diethylene glycol, triethylene glycol, tetra  ethylene glycol, polyethylene glycol, dipropylene glycol, polypropylene glycols, Dibutylene glycol and polybutylene glycols in question.

By choosing the defined excess alcohol the content of hydroxyl end groups and thus the "middle" Molecular weight n specified. Polyester are preferred used from aliphatic starting components.

Hydroxyl group-containing polyesters are, for example, those which are prepared by polymerizing a lactone, for example ε- caprolactone, or by condensing a hydroxycarboxylic acid, for example ω- hydroxycaproic acid, onto a starter containing hydroxyl groups. n arises again arithmetically as described above.

Those suitable for the process according to P 27 12 435.2 Polyester polyols preferably have 2 to 4 hydroxyl groups, particularly preferably 2 hydroxyl groups.

Carbonic acid bis-aryl ester according to P 27 12 435.2 are in particular those of the formula (I)

wherein
Ar is a substituted or unsubstituted aryl radical having 6 to 18 carbon atoms.

As substituents come in particular C₁-C₄ alkyls as well Nitro, halogen, such as chlorine or bromine, in question.  Examples of these are diphenyl carbonate, alkyl-substituted Diphenyl carbonates such as the di-toluyl carbonates, halogen-substituted Diphenyl carbonates such as di-chlorophenyl carbonates, Dinaphthyl carbonate and alkyl-substituted and halogen-substituted dinaphthyl carbonates; here can the nitro, alkyl or halogen substituents two phenyl nuclei or on both naphthyl nuclei of the diaryl carbonates be the same or different or symmetrical or be asymmetrical to each other. So there are, for example also phenyl toluyl carbonate, phenyl chlorophenyl carbonate, 2-toluyl-4-toluyl carbonate or 4-toluyl-4-chlorophenyl carbonate suitable for the process.

Bis-arylcarbonates of over -OCOO groups-extended Polyester diols according to P 27 12 435.2 are thus in particular that of the formula (II)

wherein
Ar has the meaning given above,
- (Polyester) - represents the divalent radical of one of the polyester diols described above and
n is an integer from 2 to 20, preferably 2 to 10.

Suitable catalysts for the process according to P 27 12 453.2 are basic transesterification catalysts like for example alkali or alkaline earth phenates, alkali or Alkaline earth alcoholates and tertiary amines such as  Triethylenediamine, morpholine, pyrrolidone, pyridine, triethylamine or metal compounds such as antimony trioxide, zinc chloride, Titanium tetrachloride and titanium tetrabutyl ester.

The catalyst is used in amounts between 20 ppm and 200 ppm, based on the total weight of the polyester diol used and the carbonic acid bis-aryl ester used, used.

These amounts of catalyst can, if appropriate, still fall below when using the starting products the acidic catalysts do not contain any basic impurities, and when using the basic catalysts contains no acidic impurities. In interest the lowest possible natural color of the carbonic acid esters produced of polyester diols are the smallest possible amounts of catalyst to prefer.

The method according to P 27 12 435.2 is preferred carried out in substance, i.e. in the absence of Solvent. If necessary, you can also use the Inert solvents such as aliphatic reaction conditions Hydrocarbons or aromatic hydrocarbons, which may contain nitro groups, for example will.

The reaction time depends on the reaction temperature and the type and amount of the catalyst used and is 1 to 20 hours.

The in the process according to P 27 12 435.2 emerging hydroxyaryl compounds can be finished  Reaction can be removed by discontinuous procedure the hydroxyaryl compounds during the reaction be separated by distillation. If you carry out the transesterification reaction according to a continuous procedure through, then the hydroxyaryl compounds are through fractional distillation from the reaction mixture separated.

According to a particularly preferred embodiment of the method according to P 27 12 435.2 with sodium phenolate as a catalyst in a mixture of polyester diol and carbonic acid bis-aryl esters at 110 ° C and 150 ° C, wherein less than one per OH group of the polyester diol Mol carbonic acid bis-aryl ester is used.

According to the procedure in P 27 12 435.2 thus bis-carbonic acid monoaryl esters extended by -OCOO bridges Polyester diols are shown; showed surprisingly, that the extension runs smoothly, at the same time a quantitative esterification of the terminal Hydroxyl groups takes place. It was also surprising that the monocular inconsistency of the starting polyester diols during the extension under simultaneous Esterification remains practically unchanged.

In the process according to P 27 12 435.2, the desired molecular weight n of an extended and esterified polyester diol (II) is determined by the amount of the diaryl carbonate (I) reacted with the polyester diol; it generally applies that n moles of polyester diol have to be reacted with (n + 1) moles (I) in order to obtain an n- fold polyester diol with terminal aryl carbonate groups and extended by -OCOO groups (n has the in Values given in formula (II)).

The middle ones listed in the examples below Molecular weights are number average n, the osmometric were determined, unless stated otherwise.

The Staudinger index [ η ] _{THF given} was measured in THF at 25 ° C. and is given in dl / g. For the definition of the Staudinger Index see: HG Elias: "Macromolecules", Hüthig & Wepf-Verlag, Basel, p. 265.

Examples from P 27 12 435.2

1. 800 parts by weight of a polyester diol from hexane-1,6-diol and adipic acid with an average molecular weight n = 800 (determined from the OH number measurement), 321 parts by weight of diphenyl carbonate and 0.1 part by weight of sodium phenolate are heated with stirring, nitrogen and a vacuum of 8 mbar for 2 hours at 110 ° C, 2.5 hours at 130 ° C and 3 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 / 0.13 mbar in a thin film evaporator. A colorless, viscous oil with an average molecular weight n of 1820 is obtained. The OH number is zero; the Staudinger index [ η ] _THF is 0.078.

2. 2000 parts by weight of a polyester diol from adipic acid and equal molar amounts of ethylene glycol and butane-1,4-diol of average molecular weight n = 2000 (determined from the OH number measurement). 321 parts by weight of diphenyl carbonate and 0.12 part by weight of sodium phenolate are stirred for 2.5 hours at 110 ° C., 2 hours at 130 ° C. and 2.5 hours at 160 ° C. with stirring, nitrogen and a vacuum of 4 mbar heated. During this time, phenol is distilled off from the reaction mixture. If desired, residual traces of phenol can then be separated off at 110 ° C / 0.13 mbar in a thin-film evaporator. A colorless viscous oil with an average molecular weight n of 4240 and a Staudinger index [ η ] _THF of 0.114 is obtained. The OH number is zero.

3. 2000 parts by weight of a polyester diol from adipic acid and a mixture of hexane-1,6-diol / neopentyl glycol in a molar ratio of 65/35 from the average molecular weight n 2000 (determined by OH number measurements) 321 parts by weight of diphenyl carbonate and 0.12 part by weight of sodium phenolate are heated with stirring, nitrogen and a vacuum of 2.7 mbar for 2.5 hours at 110 ° C., 3 hours at 140 ° C. and 3 hours at 1.5 ° 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 / 0.13 mbar in a thin film evaporator. A colorless, viscous oil is obtained which solidifies into a wax after a while and has an average molecular weight n of 4,240. The Staudinger index [ η ] _THF is 0.25 and the OH number is zero.

4. 2000 parts by weight of a polyester diol from adipic acid and a mixture of hexane-1,6-diol / neopentyl glycol in a molar ratio 65/35 of average molecular weight n 2000 (determined by OH number measurement). 285 parts by weight of diphenyl carbonate and 0.12 part by weight of sodium phenolate are heated with stirring, nitrogen and a vacuum of 2.7 mbar for 4 hours at 110 ° C., 3 hours at 140 ° C. and 5 hours at 155 ° 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 / 0.13 mbar in a thin film evaporator. A colorless wax with an average molecular weight n of 6270 is obtained. The Staudinger index [ η ] _THF is 0.32 and the OH number is zero.

5. 2000 parts by weight of a polyester diol from adipic acid and a mixture of hexane-1,6-diol / neopentyl glycol in a molar ratio of 65/35 from the average molecular weight n 2000 (determined by OH number measurement), 267.5 parts by weight. Parts of diphenyl carbonate and 0.12 part by weight of sodium phenolate are stirred, under nitrogen and under a vacuum of 1.33 mbar for 3 hours at 110 ° C., 5 hours at 140 ° C., 2 hours at 150 ° C. and 1 hour at 165 ° C heated. 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 / 0.13 mbar in a thin-film evaporator. A colorless wax with an average molecular weight n 8290 is obtained. The Staudinger index [ η ] _THF is 0.40 and the OH number is zero.

For the production according to the invention of those extended via carbonate groups Polyester diol bis-diphenol carbonates suitable diphenols are:

Hydroquinone
Resorcinol
Dihydroxydiphenyls
Bis (hydroxyphenyl) alkanes
Bis (hydroxyphenyl) cyclocalalkanes
Bis (hydroxyphenyl) sulfides
Bis (hydroxyphenyl) ether
Bis (hydroxyphenyl) ketones
Bis (hydroxyphenyl) sulfoxides
Bis (hydroxyphenyl) sulfones
α , α- bis (hydroxyphenyl) diisopropylbenzenes

and their nuclear alkylated and nuclear halogenated compounds. These and other suitable aromatic dihydroxy compounds are z. B. in the US patents 30 28 365, 29 99 835, 31 48 172, 32 71 368, 29 91 273, 32 71 367, 32 80 078, 30 14 891 and 29 99 846 and den German Offenlegungsschriften 20 63 050, 22 11 957.  

Suitable diphenols are, for example

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

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.

Those which are suitable according to the invention are extended via carbonate groups Diphenols can be used alone as well as several be used.

According to the invention extended through carbonate groups Polyesterdiol-bis-diphenol carbonates are thus, for example that of the formulas (IVa-IVh):

wherein - (polyester) - the divalent radical in the formulas (IVa-IVh) the polyester diols described on page 10-11.

The invention extended over carbonate groups Polyesterdiol-bis-diphenol carbonates can be used as starting bisphenols in the production of polycarbonates according to the known Two-phase interfacial polycondensation process be used. Polyester-polycarbonates are thus obtained of a certain structure.  

The polyester-polycarbonates obtained according to the invention are characterized by the presence of an amorphous (soft) Polyester phase and a crystalline (hard) polycarbonate phase or an amorphous-crystalline (hard) polycarbonate phase.

From a morphological point of view the polyester polycarbonates two different, spatially separated phases d. H. Areas on that is made up of a continuous amorphous Polyester phase and a crystalline or amorphous crystalline Assemble the polycarbonate phase.

The high molecular, segmented thermoplastically processable Polyester polycarbonates made from over Carbonate group-extended polyester diol bis-diphenol carbonates, show compared to other polyester polycarbonates, for example also compared to those of the German patent application P 27 26 376.9 additional advantages, such as e.g. B. an even better phase separation, the better application properties of the corresponding Polyester polycarbonates leads.

The polyester-polycarbonates obtained according to the invention have due to their multi-phase better heat resistance as comparable single-phase polyester polycarbonates.

Single-phase polyester polycarbonates are for example in US 31 51 615. You are after ver  different processes available, but preferably after the "pyridine process" known from polycarbonate production.

The production of two-phase polymers, for example of polycarbonate-polycaprolactones has so far only been successful using bischloroformic acid esters of polycaprolactones and Polycarbonate oligomers (see FR-PS 22 35 965).

The same applies to those although not as two-phase designated polyester-polycarbonates DE-AS 11 62 559.

The use according to the invention of the carbonate groups extended according to the invention Polyester diol bis-diphenol carbonates has opposed to the use of appropriate Bischloroformic acid esters have the advantage of being insensitive to hydrolysis and therefore better storability and clear bifunctional reactivity.

The polyester-polycarbonates obtained according to the invention have in particular due to their crystalline polycarbonate phase improved heat resistance.

The recognition of the different phases of the invention Polyester-polycarbonates are possible with the help of differential thermal analysis, for example the polyester phase has a freezing temperature <20 ° C, the amorphous fraction a freezing temperature between Has 100 ° C and 150 ° C and the crystalline portion of the polycarbonate phase a crystallite melting point between 170 ° C and 250 ° C.  

The high molecular, segmented, thermoplastically processable Polyester-polycarbonate, manufactured after Process according to the invention, in addition to the special thermal resilience good transparency, highly elastic Behavior and excellent elongation at break of <400%.

The for the production of the polyester-polycarbonates according to the invention from those according to the invention extended over carbonate groups Suitable polyester di-bis-diphenol carbonates other diphenols are already used for the production of about carbonate group-extended polyester diol bis-diphenol carbonates on pages 18-19 of this patent application, in particular that of formula (III) from page 7 of this patent application; are suitable, for example

4,4'-dihydroxy-diphenyl
Bis (4-hydroxyphenyl) methane
2,4-bis (4-hydroxyphenyl) -2-methylbutane
α , α -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.

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

The chain length of the polyester polycarbonates can be added a chain terminator, e.g. B. a monofunctional Phenols such as phenol, 2,6-dimethylphenol, p-bromophenol or p-tert-butylphenol can be set, with per mole of Diphenol used between 0.1 and 10 mol% chain terminators can be used.

If necessary, the chain length of the polyester polycarbonates for example by adding polyester monool mono-diphenol carbonates in molar amounts or on moles used polyester diol bis-diphenol carbonates extended via carbonate groups, adjusted up to about 50 mol% will.

The inventive production of the high molecular weight segmented, thermoplastically processable polyester-polycarbonates takes place, as already mentioned, after the two-phase interface Polycondensation process. To do this, use one of the aforementioned other diphenols or mixtures of the aforementioned other diphenols dissolved in alkaline aqueous solution. Likewise, the carbonate groups according to the invention are extended Polyester diol bis-diphenol carbonates, in particular those of the formula (IV), or mixtures thereof in one inert organic solvents immiscible with water solved and added. 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 initiated. The polycondensation takes place after the phosgenation by adding 0.2-10 mol% of tertiary aliphatic amine, based on moles of diphenol. This is for phosgenation Times between 5 minutes and 90 minutes for polycondensation Times between 3 minutes and 3 hours required.  

The resulting solutions of polyester-polycarbonates in the organic solvents are analogous to the solutions of manufactured by the two-phase interface process thermoplastic polycarbonates worked up, the Polyester-polycarbonates are also post-treated, and while they will 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 leave or
• b) in the insulation, for example in the evaporation extruder already subject to shear forces, or
• c) before isolation in the manufacture of the polyester polycarbonates according to the two-phase interface method Allow the solvent used to gel.

As an inert organic solvent for the invention Manufacturing processes of polyester-polycarbonates are water-immiscible aliphatic chlorinated hydrocarbons such as methylene chloride, chloroform and 1,2-dichloroethane, or chlorinated aromatics, such as chlorobenzene, dichlorobenzene and chlorotoluene or mixtures thereof Suitable solvents.

As alkaline aqueous solutions for the invention Processes are suitable solutions of Li (OH) ₂, NaOH, KOH, Ca (OH) ₂ and / or Ba (OH₂) in water.  

As tertiary aliphatic amines for the invention Processes with 3 to 15 carbon atoms are suitable, for example trimethylamine, triethylamine, n-tripropylamine and n-tributylamine and varies depending on the used Diphenol between 0.2-5 mol% when using tetramethyl-substituted diphenols between 5-10 mol%, based on the total amount of diphenols used (= respective sum of carbonate group-extended Polyesterdiol-bis-diphenol carbonates and others Diphenols).

Those produced by the process according to the invention Polyester-polycarbonates can be made by the following methods be isolated:

• a) By distilling off the organic solvent to to a certain concentration, being a high percentage (about 30-40 wt .-%) polymer solution during the subsequent slow evaporation the remaining solvent gels the polyester polycarbonate.
• b) By precipitation of the polyester-polycarbonates from the organic Phase with organic solvents, whereby to precipitate, for example, methanol, ethanol, Isopropanol, acetone, aliphatic hydrocarbons and Cycloaliphatic hydrocarbons are suitable.
• c) by isolating the polyester polycarbonates in the evaporation extruder, at temperatures of around 160-240 ° C under the conditions known for polycarbonate extrusion and using shear forces.

The gelation of the process according to the invention manufactured polyester polycarbonates, be it without insulation in the processed organic phase of the Two-phase reaction mixture or in a separate solution the previously isolated polyester polycarbonates in organic Solvents, done by cooling the high-proof Polymer solution, whereby for the gelation depending on the polyester or polycarbonate content times between 5 minutes and 12 hours at temperatures between 0 ° C and 40 ° C.

The gelled product can be worked up to a powder grain mixture be, the polyester-polycarbonate obtained 48 hours at 50 ° C and 24 hours at 100 ° C in a vacuum is dried.

As a solvent for the separate gelation of the isolated Polyester polycarbonates are suitable for organic solvents such as methylene chloride, benzene, toluene or Xylene.

The insulated polyester 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 polyester polycarbonates takes 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 effect and the reaction temperature between can be about 0 ° C and about 80 ° C, and is in generally 1.1-3.0 moles of phosgene per mole of diphenol.  

The implementation of the invention according to the Carbonate group-extended polyester diol bis-diphenol carbonate with diphenols and with phosgene using the two-phase interface method is quantitative; thus determined the respective reactant ratio of over Carbonate group-extended polyester diol bis-diphenol carbonate to other diphenol from the polycarbonate portion and the polyester content of the polyester polycarbonates to be synthesized.

The polycarbonate content in the process according to the invention produced polyester polycarbonates, depending according to the desired property profile, approximately between 35 and 80 % By weight, the hardness increasing with the proportion of polycarbonate and heat resistance increases and the elasticity and Elongation at break decreases.

As the polycarbonate fraction of the polyester polycarbonates obtained according to the invention is the amount by weight of aromatic Polycarbonate structural units of the following formula (V)

where D for the diphenolate residues in polyester polycarbonate stands, especially on aromatic polycarbonate structural units to understand the formula (IIIa)

wherein X and Y₁ to Y₄ the formula (III) meaning to have.  

As the polyester fraction of the polyester polycarbonates obtained according to the invention is consequently the amount by weight of carbonate groups Polyester diolate block units one of the on page 9-11 described polyester diols the simplified Formula (VI)

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

Polyester polycarbonates obtained according to the invention are, for example those that are 30 to 95 wt .-%, preferably 35 to 80 wt .-% of polycarbonate structural units Formula IIIb exist

wherein
Y is H, Cl, Br or CH₃, and consist of 70 to 5% by weight, preferably 65 to 20% by weight, of polyester diolate block units extended via carbonate groups.

The polyester polycarbonates obtained according to the invention should have average molecular weights w (weight average) of 25,000 to 250,000, preferably 40,000 to 150,000, determined by the light scattering method with the scattered light photometer. The relative solution viscosities η _rel. (measured on 0.5 g in 100 ml CH₂Cl₂ at 25 ° C) of the polyester polycarbonates according to the invention are between 1.3 and 3.0, preferably between 1.4 and 2.6.

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

This differentiation of the glass transition temperature from the freezing temperature and the crystallite melting temperature the polycarbonate content is characteristic for the presence of phase separation of polyester and polycarbonate content.

The partial crystallinity, detectable by a measurable Enthalpy of fusion of the polycarbonate portion of the invention Polyester polycarbonates that are at least 1-8 cal / g Polymer amounts can by stretching and by the mentioned subsequent tempering (5 min. to 25 hours) at 40-170 ° C or by the aforementioned action of shear forces during thermoplastic processing in a multi-screw extruder still be increased by 50%, the heat resistance of the products increases, the appearance of transparent after opaque to opaque changes.

The semi-crystalline elastic polyester-polycarbonates can in each case below or in the area of the crystallite melting point of the crystalline polycarbonate content  Temperatures from 130 ° C to max. 250 ° C processed thermoplastic be a substantial part of the crystallinity is not lost. At processing temperatures above the crystallite melting point of the crystalline polycarbonate portion you get amorphous, transparent products.

The crystalline portion of the polycarbonate portion of the invention polyester polycarbonates obtained can thus be varied and is a good heat resistance for practice to have the polyester polycarbonate at about 1-8 cal / g Polymer, preferably at 2.5-5.5 cal / g polymer.

The processing and isolation according to the invention takes place the polyester-polycarbonates without tempering, without gelling and without the action of shear forces, you get single-phase Polyester-polycarbonates, i.e. such products only a freezing temperature measurable by differential thermal analysis.

The UV stability and hydrolysis stability of the invention polyester polycarbonates obtained can be improved due to the usual amounts for thermoplastic polycarbonates UV stabilizers such as substituted "Benzophenone" or "Benztriazole", by hydrolysis protection agents, such as mono- and especially polycarbodiimides, (cf. W. Neumann, J. Peter, H. Holtschmidt and W. Kallert, Proceeding of the 4th Rubber Technology Conference, London, 22-25 May 1962, pp. 738-751) in Quantities of 0.2-5 wt .-%, based on the weight of the Polyester polycarbonate, and by in the chemistry of thermoplastic Polyester and thermoplastic polycarbonates known anti-aging agents.  

To modify the products obtained according to the invention substances such as soot, kieselguhr, kaolin, Clays, CaF₂, CaCO₃, aluminum oxides and conventional glass fibers in amounts of 2 to 40 wt .-%, based on each Total weight of the molding compound and inorganic pigments both as fillers as well as nucleating agents be added.

If flame-retardant products are desired, approx. 5 to 15% by weight, based on the weight of the polyester polycarbonates, in the chemistry of thermoplastic Known polyester and thermoplastic polycarbonates Flame retardants such as B. antimony trioxide, tetrabromophthalic anhydride, Hexabromocyclododecane, tetrachlor or tetrabromobisphenol-A or tris (2,3-dichloropropyl) phosphate are added, being in the polycarbonate proportions of the polycarbonates according to the invention statistically built-in tetrachloro- and tetrabromobisphenols also show flame retardant properties.

Furthermore, in the chemistry of thermoplastic polyesters and thermoplastic polycarbonates known processing agents, like release aids, in effective Way to be used.

Those obtained by the process according to the invention Polyester-polycarbonates can be beneficial anywhere be applied where a combination of hardness and Elasticity, especially desired from cold flexibility is, e.g. B. in body construction, for the production of low-pressure tires for vehicles, for wrapping hoses, Plates, tubes and for flexible drive pulleys.  

The middle ones listed in the following examples Molecular weights are number average n and by determination the OH number determined.

The Staudinger index [ h ] given in example A was measured in THF at 25 ° C. and stated in dl / g.

For the definition of the Staudinger index see: H. G. Elias: "Macromolecules", Hüthig & Wepf-Verlag Basel, P. 265.

The relative solution viscosity η _{rel of} the examples C₁-C₄ is defined by the viscosity of 0.5 g polyester polycarbonate in 100 ml methylene chloride at 25 ° C.

The tensile strength and the elongation at break were in accordance with DIN 53 455 or 53 457 measured.

Gel chromatographic studies were carried out in tetrahydrofuran with styragel columns (separation range 1.5 × 10⁴ nm, 1 × 10⁴ nm, 3 × 10³ nm and 2 × 10² nm) at room temperature.

The calibration of bisphenol A polycarbonate was used for the determination. There were no major discrepancies in the comparison to w determination determined using the light scattering method.

The differential thermal analysis (DTA) was carried out with the device, "DuPont, model 900". To interpret the Freezing temperature became the approximate middle of the softening range according to the tangent method and for the Crystallite melting point is the approximate center of the endothermic Peaks of the melting curve selected.  

Example A Preparation of a carbonate group-extended polyester diol bis-phenyl carbonate

2000 parts by weight of a polyester diol from adipic acid and a mixture of hexane-1,6-diol / neopentyl glycol in a molar ratio of 65/35 from the average molecular weight n 2000 (determined by OH number measurement). 285 parts by weight of diphenyl carbonate and 0.12 part by weight of sodium phenolate are heated with stirring, nitrogen and a vacuum of 2.7 mbar for 4 hours at 110 ° C., 3 hours at 140 ° C. and 5 hours at 155 ° 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 / 0.13 mbar in a thin film evaporator. A colorless wax with an average molecular weight n of 6270 is obtained. The Staudinger index [ η ] _THF is 0.32 and the OH number is zero.

Example B 1 Preparation of a carbonate group extended Polyesterdiol bis (bisphenol A) carbonate, which still contains 2.6% by weight of bisphenol A.

313.5 parts by weight of bisphenyl carbonate, one extended via carbonate groups Polyester diols from adipic acid and a mixture of 1,6-hexanediol, neopentyl glycol in molar Ratio 65/35 of the average molecular weight n 6270, and which was prepared according to Example A, 29.7 Parts by weight of 2,2-bis (4-hydroxyphenyl) propane (bisphenol A) and 0.03 part by weight of catalyst (sodium bisphenolate of bisphenol  A to bisphenol A = 1: 100) with stirring and Nitrogen atmosphere first at 125 ° C for 1 hour, then Heated for 4 hours at 150 ° C and 0.07 mbar. During this 8.1 parts by weight of phenol are distilled off over a period of time. You get a colorless wax.

Example B 2 Preparation of a carbonate group extended Polyesterdiol bis (bisphenol A) carbonate, which still contains 3.6% by weight of bisphenol A.

297 parts by weight of bisphenyl carbonate, one extended via carbonate groups Polyester diols from adipic acid and a mixture of hexanediol-1,6 / neopentylglycol in molar Ratio 65/35 of average molecular weight n 4240, and that was prepared according to Example A, 41.5 parts by weight 2,2-bis (4-hydroxyphenyl) propane (bisphenol A) and 0.1 part by weight Sodium phenolate are stirred and under a nitrogen atmosphere first 1 hour at 125 ° C, then Heated for 4 hours at 150 ° C and 1.1 mbar.

During this time, 11.2 parts by weight Phenol distilled off.

Example B 3 Production of a carbonate group-extended polyester diol bis-diphenol carbonate of the formula (IV f), which also contains 2,2-bis (3,5-dimethyl-4-hydroxyphenyl) propane in amounts of 4.6% by weight

297 parts by weight Bisphenyl carbonate one extended over carbonate groups Polyester diols from adipic acid and one Mixture of 1,6-hexanediol / neopentyl glycol in molar ver  ratio 65/35 of average molecular weight n 4240, and which was prepared according to Example A, 51.8 parts by weight 2,2-bis (3,5-dimethyl-4-hydroxyphenyl) propane and 0.26 part by weight Catalyst (bisphenol A sodium bisphenolate: Bisphenol A = 1: 100) with stirring and nitrogen atmosphere first 1 hour at 125 ° C, then 5 hours at 150 ° C and 0.27 mbar heated. During this time 9.8 parts by weight of phenol distilled off.

Example B 4 Preparation of a carbonate group extended Polyesterdiol-bis-diphenol carbonate of the formula (IV f), the Contains 2,2-bis (3,5-dimethyl-4-hydroxyphenyl) propane in amounts of 3.1% by weight

313.5 parts by weight Bisphenyl carbonate one extended over carbonate groups Polyester diols from adipic acid and one Mixture of 1,6-hexanediol / neopentyl glycol in molar Ratio 65/35 of average molecular weight n 6270, and which was prepared according to Example A, 37 wt .-% 2,2- Bis- (3,5-dimethyl-4-hydroxyphenyl) propane and 0.19 part by weight Catalyst (bisphenol A sodium bisphenolate: bisphenol A = 1: 100) with stirring and nitrogen atmosphere first 1 hour at 125 ° C, then 5.5 hours at 150 ° C and 0.27 mbar heated. During this time 7.4 parts by weight Phenol distilled off.

Example C 1 Production of a polyester polycarbonate with 50 wt .-% polyester

110.6 parts by weight of this viscous oil from Example B1  in 1725 parts by weight Methylene chloride, become a solution of 80 parts by weight Bisphenol A and 1.77 parts by weight p-tert-butylphenol in 70 parts by weight 45 percent NaOH and 1300 parts by weight least water given. Within 30 minutes at 20-25 ° C Stirring and nitrogen atmosphere 58.3 parts by weight Phosgene introduced. During the introduction, 126 parts by weight are simultaneously 45 percent NaOH added dropwise so that the pH is constant stays at pH 13. After introducing phosgene, 39.8 Parts by weight a 1 percent Triethylamine solution added and Stirred for 1 hour. The organic phase is separated, one after the other with 2 percent phosphoric acid and finally with dist. Washed water until electrolyte-free. After separating the water, the organic phase be worked up according to the following procedures:

• C.1.1 By distilling off the CH₂Cl₂ to a certain Concentration or by adding chlorobenzene to the organic Phase and distilling off all methylene chloride receive a high percentage (about 30-40 wt .-%) polymer solution. By then slowly evaporating the residual methylene chloride or chloride benzene gelled the polyester polycarbonate and can form a powder-grain mixture be worked up further. The polyester polycarbonate obtained is 48 hours at 50 ° C and 24 hours dried at 100 ° C in a vacuum.
• C.1.2 By distilling off the solvent, drying in Vacuum drying cabinet at about 80-110 ° C and 20 mbar and subsequent A finely divided solid product is obtained by grinding.
• C.1.3 By precipitating the polyester polycarbonate from the organic Phase with, for example, methanol, ethanol, isopropanol, Acetone, aliphatic hydrocarbons and  cycloaliphatic hydrocarbons and subsequent Drying in a vacuum drying cabinet at 80-110 ° C and 20 mbar.
• C.1.4 By concentrating the organic phase in the evaporation extruder and subsequent extrusion at about 160-240 ° C below that for the conditions known for polycarbonate extrusion.

The rel. Viscosity of the polyester polycarbonate obtained according to C.1.1-C.1.4 is η _rel = 1.63 (measured in CH₂Cl₂ at 25 ° C and d = 5 g / l). According to gel-chromatographic determination, the polyester-polycarbonate shows a maximum at 40,000. It has 50% by weight of polyester and 50% by weight of polycarbonate. Some mechanical properties of a film cast from methylene chloride are:
Tensile strength 26.9 (MPA) (measured according to DIN 53 455)
Elongation at break 366% (measured according to DIN 54 455)

The granulated polyester-polycarbonate shows after differential thermal analysis a glass transfer temperature (freezing temperature) of the polyester portion of -38 ° C, a glass transition temperature (Freezing temperature) of the amorphous Polycarbonate content of 120 ° C and a crystallite melting point of the crystalline polycarbonate content of approx. 190 ° C. The enthalpy of fusion of the crystalline polycarbonate portion is between 2.5 and 5.5 cal / g polymer.

Example C 2 Production of a carbonate group-extended polyester-polycarbonate with 50% by weight of polyester

115.1 parts by weight of the viscous oil from Example B 2, dissolved in 1725 parts by weight Methylene chloride becomes a solution of 75.2 parts by weight Bisphenol A and 1.18 parts by weight p-tert-butylphenol in 1300 parts by weight least Water and 70 parts by weight 45 percent Given sodium hydroxide solution.

A solution of 0.52 parts by weight is 1,4-bis- (4 ′, 4 ′ ′ - dihydroxytriphenylmethyl) benzene and 45 parts by weight 5 percent Sodium hydroxide solution added.

58.3 parts by weight are produced within 40 minutes. Phosgene introduced while stirring and under a nitrogen atmosphere, while at the same time 135 parts by weight 45 percent Sodium hydroxide solution are added dropwise to keep pH 13 constant. After introducing phosgene, 0.4 parts by weight Triethylamine added. The approach becomes more viscous. After 1 hour, the organic phase is separated off and the polyester polycarbonate is recovered as described in Example C 1 (workup C _1.1 -C _1.4 ).

The rel. Viscosity of the polyester polycarbonate is η _rel = 1.71 (in CH₂Cl₂).

After determination by gel chromatography, the polymer shows Maximum at 45,000 and a secondary maximum at 200,000.

The mech. Properties of a film cast from methylene chloride with 50% by weight polyester and 50% by weight polycarbonate are:
Tear resistance: 20.1 MPA
Elongation at break: 426%

The granulated polyester-polycarbonate shows after differential thermal analysis a glass transfer temperature (freezing temperature) of the polyester content of -34 ° C, a glass over  transition temperature (freezing temperature) of the amorphous polycarbonate portion of 125 ° C and a crystallite melting point of the crystalline polycarbonate content of approx. 185 ° C. The Enthalpy of fusion of the crystalline polycarbonate portion is between 2.5 and 5.5 cal / g polymer.

Example C3 Production of a polyester polycarbonate from 2,2-bis (3,5-dimethyl-4-hydroxyphenyl) propane with 50% by weight polyester

118.0 parts by weight of the viscous oil from Example B 3 and 0.6 Parts by weight Tributylamine (= 1 mole% per mole of bisphenol units), dissolved in 1725 parts by weight Methylene chloride become one Solution of 73.5 parts by weight 2,2-bis (3,5-dimethyl-4-hydroxyphenyl) propane in 57.3 parts by weight 45 percent Sodium hydroxide solution and 1300 parts by weight distilled water.

Within 30 min. With stirring and nitrogen atmosphere 95.6 parts by weight Phosgene initiated while at the same time 225 parts by weight 45 percent Sodium hydroxide solution to keep it constant be added dropwise from pH 13. After introducing phosgene 5.4 parts by weight for complete condensation Tributhylamine (= 9 mol% per mol bisphenol units) added. The approach becomes more viscous. After 3 hours, the organic is separated Phase and wins the polyester polycarbonate as described in Example C 1 (workup C 1.1).

The rel. Viscosity of the polyester polycarbonate is η _rel = 1.55 (in CH₂Cl₂).

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

112.5 parts by weight of the viscous oil from Example B 4 and 0.6 Parts by weight Tributylamine (= 1 mole% per mole of bisphenol units), dissolved in 1725 parts by weight Methylene chloride, become one Solution of 79.5 parts by weight 2,2-bis (3,5-dimethyl-4-hydroxyphenyl) propane in 57.3 parts by weight 45 percent Caustic soda and 1300 parts by weight least Given water. Be within 30 minutes with stirring and nitrogen atmosphere 95.6 parts by weight Phosgene initiated while 235 parts by weight 45 percent Caustic soda added dropwise to keep pH 13 constant. After introducing phosgene, condensation is complete 5.4 parts by weight Tributylamine (= 9 mole% per mole of bisphenol units) admitted. The approach becomes more viscous. To The organic phase is separated off for 3 hours and won Polyester-polycarbonate as in example C 1 (workup C 1.1) described.

The rel. Viscosity of the polyester polycarbonate is η _rel = 1.68 (in CH₂Cl₂).

Claims (6)

1. A process for the preparation of carbonate group-extended polyester diol bis-diphenol carbonates, characterized in that polyester polyols with molecular weights n (number average) over 250, with carbonic acid bis-aryl esters at temperatures between 100 ° C and 200 ° C in a vacuum below 46.6 mbar in the presence of alkali or alkaline earth phenolates in amounts of 20 ppm to 200 ppm, based on the total weight of the polyester diol and carbonic acid bis-aryl ester used, heated, with less per OH group of the polyester polyol are used as 1 mol of carbonic acid bis-aryl ester and the resulting hydroxyaryl compound is distilled off, and the polyester diol bis-aryl carbonates obtained which have been lengthened via carbonate groups and diphenols at temperatures between 100 ° C. and 200 ° C. in vacuo below 46.6 mbar in the presence of alkali or alkaline earth phenolates in amounts of 10 ppm to 200 ppm, based on the total weight of the carb onate group-extended polyester diol bis-aryl carbonate and the diphenol used in each case, with more than 1 mol of diphenol being used for a carbonic acid aryl ester group of the polyester diol bis-aryl carbonate extended via carbonate groups and the resulting hydroxyaryl compound being distilled off. 2. The method according to claim 1, characterized in that that the obtained over carbonate groups-extended Polyester di-bis-aryl carbonates together with excess carbonic acid bis-aryl ester Implemented diphenols. 3. Carbonate group-extended polyester diol bis-diphenol carbonates obtained according to the method of claim 1. 4. Carbonate group-extended polyester diol bis-diphenol carbonates of the formula IV wherein
- (Polyester) - the divalent residue of the reaction product of one or more dibasic alcohols with one or more dibasic carboxylic acids is to be understood,
n is an integer from 2 to 20, preferably 2 to 10, Y₁ and Y₄ are the same or different and are hydrogen or halogen, obtained according to the process of claim 1. 5. Process for the production of polyester-polycarbonates, characterized in that the carbonate groups were extended Polyesterdiol-bis-diphenol carbonates of the claims 3 and 4, with other diphenols, monofunctional Phenols as chain terminators and with phosgene in one Liquid mixture of inert organic solvents and alkaline aqueous solution at temperatures between 0 ° C and 80 ° C at a pH between 9 and 14, and after adding phosgene by adding 0.2 mol% to 10 mol% of tertiary aliphatic Amine, based on the molar amount of diphenol, polycondensed, being the weight ratio of over Carbonate group-extended polyester diol bis-diphenol carbonate to other diphenol from the polycarbonate portion and the polyester content of the polyester polycarbonates becomes. 6. The method according to claim 5, characterized in that as other diphenols those of the formula (III) be implemented in what Y₁ to Y₄ are the same or different and are hydrogen or halogen.