DE2726417A1 - METHOD FOR PRODUCING CARBONIC ACID TO DIPHENOL ESTERS OF POLYESTER DIOLS EXTENDED THROUGH CARBONATE GROUP AND USE THEREOF FOR PRODUCING HIGH MOLECULAR, SEGMENTED, THERMOPLASTIC PROCESSABLE POLYESTER POLYCARBONATES - Google Patents

Description

Bayer Aktiengesellschaft

Central Patent Department «. Trademarks and licenses

509 Leverkusen. Bayerwerk

PS / AB

June 10, 1977

Process for the production of carbonic acid bis-diphenol esters of polyester diols elongated via carbonate groups and their use for the production of high molecular weight, segmented, thermoplastically processable polyester-polycarbonates

The German patent application P 2 712 435.2 (Le A 17 840) claims a process for the preparation of carbonic acid aryl esters of polyester polyols elongated via carbonate groups from polyester polyols with Mn about 25O, preferably over 600, and carbonic acid bisaryl esters, which thereby is characterized in that one polyester polyols with molecular weights Mn (number average) over 250, preferably at Temperatures between 100 ° C. and 200 ° C. in vacuo below 35 torr together with carbonic acid bis-aryl esters in the presence heated by catalysts, less than one mole of carbonic acid bis-aryl ester being used per OH group, and the resulting hydroxylaryl compound is distilled off.

Particularly suitable polyester polyols are reaction products of polyvalent, preferably divalent, and optionally trihydric alcohols with polybasic, preferably dibasic, carboxylic acids are also suitable.

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The present invention now relates to the use of the according to the above-mentioned German patent application P 2 712 435 (Le A 17 840) available carbonic acid aryl esters for the preparation of carbonate groups-extended Polyester diol bis diphenol carbonates, another subject of the present invention are the polyester diol bis-diphenol carbonates obtained according to the invention and lengthened via carbonate groups and their use for the production of polyester-polycarbonates. Another item of the present invention are the polyester-polycarbonates obtained according to the invention with an improved Phase separation between soft segment and hard segment, which leads to better application properties of the corresponding Polyester-polycarbonate leads.

The transesterification of the polyester diol bis-aryl carbonates which are obtainable via carbonate group-extended according to German patent application P 2 712 435.2 (Le A 17 840) with excess diphenols to give the corresponding polyester diol bis-diphenol carbonates which have been extended via carbonate groups takes place surprisingly smoothly without side reactions even at reaction temperatures of up to 20O ⁰ C. Neither does the molecular distribution of the starting products change, nor does polyester polyols re-form, nor does polycondensation to form polycarbonates take place.

The method according to the invention is characterized in that polyester diol bis-aryl carbonates which have been extended via carbonate groups, which according to German patent application P 2 712 435.2 (Le A 17 840) are obtainable in that polyester diols with molecular weights Mn (number average) above 250, preferably above 600, with carbonic acid bisaryl esters at temperatures between 100 ° C and 200 ° C,

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preferably between 110 C and 180 C, in a vacuum below 35 Torr, preferably between 25 Torr and 1 Torr, heated in the presence of catalysts, per OH group of the polyester diol, less than one mole of carbonic acid bisaryl ester and the corresponding hydroxyaryl compound are used is distilled off, with diphenols at temperatures between 100 C and 200 C, preferably between 110C and 180C in vacuo below 35 torr, preferably between 25 torr and 0.1 torr, heated in the presence of catalysts, for an aryl carbonate group of the polyester diol bisaryl carbonate extended via carbonate groups 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 polyester diol-bis-diphenol carbonates which have been extended via carbonate groups, obtained by this process according to the invention.

In particular, those according to German patent application P 2 712 435.2 (Le A 17 840) are made from polyester diols and carbonic acid bis aryl esters of the formula I

Ar-O-C-O- Ar, (I)

Il

Ar is a substituted or unsubstituted aryl radical with 6 to 18 carbon atoms, preferably phenyl, obtainable via carbonate groups-extended Polyesterdiol-bis-arylcarbonate of the simplified Formula II

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Ar-O-C

0- (polyester) -O-C

O-Ar,

(ID

wherein

- (Polyester) - represents the divalent radical of a polyester diol, η an integer from 2 to 20, preferably to 10, means, and

has the meaning given for the formula I, with the diphenols of the following formula III

(III)

CH

ι -

wherein X -CH ₉ -, -C-,

CH,

, 0, S or SO- mean, and

Y ₁ to

are identical or different and are hydrogen or halogen, such as, for example, chlorine or Bromine, mean to those extended by carbonate groups Polyesterdiol-bis-diphenol carbonates of the simplified formula IV implemented

-0-CfO- (polyester)

-0-C

-X

-OH, (IV)

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-Xb

wherein -Polyester-, η, X and Y _{1 have} the meanings given for the formulas II and III.

Suitable catalysts for the inventive preparation of the polyester diol bisdiphenol 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, for example, triethylenediamine, morpholine, pyrrolidine, triethylamine and tributylamine and pyridine 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 each via carbonate group-extended polyester diol bis-aryl carbonate and the diphenol used in each case.

These amounts of catalyst can, if appropriate, still be exceeded if the starting materials are used of the acidic catalysts no basic impurities, and no acidic impurities when using the basic catalysts Contain impurities. In the interests of the lowest possible inherent color of the products according to the invention to prefer the lowest possible amounts of catalyst.

The inventive method for producing the over Carbonate group-extended polyester diol bis-diphenol carbonates takes place preferably in the absence of solvents for the reactants, in particular in bulk. Possibly solvents which are inert under the reaction conditions, such as aliphatic carbon

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Hydrogen, aromatic hydrocarbons that are unsubstituted or can be substituted, for example, by nitro groups.

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

The polyester-diol-bis-diphenol-carbonates which have been lengthened via carbonate groups are produced, for example by using a mixture of polyester diol bis-phenyl carbonate which has been extended via carbonate groups obtained according to German patent application P 2 712 435.2 (Le A 17 840), a diphenol and catalyst in vacuo heated to temperatures between 100 ° C. and 200 ° C., preferably between 110 and 180 ° C., and that as the temperature progresses Phenol formed in the reaction is distilled off from the reactor. Here the diphenol is in excess used, with per carbonic acid phenyl ester group of the polyester diol bis-phenyl carbonate more than one mole Diphenol can be used, preferably between 1.1 moles and 2 moles of diphenol are used. According to one particular preferred embodiment is the reaction of a bisphenol A as a catalyst with the disodium phenolate via carbonate groups-extended polyester diol bis-phenyl carbonate, obtained according to P 2 712 435.2 (Le A 17 840), and bisphenol A in the molar ratio of bisphenyl carbonate to bisphenol A of 1: 3, at 150 C, implemented in a vacuum between 25 and 0.1 Torr.

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For the production according to the invention of those lengthened via carbonate groups Polyester diol bis-diphenol carbonates necessary via carbonate groups extended polyester diol bis-aryl carbonates are produced according to German patent application P 2 712 435.2 (Le A 17 840). From this patent application the following part is adopted:

The subject of German patent application P 2 712 435.2 (Le A 17 840) is a process for the preparation of bis-carbonic acid monoaryl esters of polyester diols extended over -OCOO groups with Mn over 250, preferably over 600, and carbonic acid bis-aryl esters, characterized in that one polyester diols having molecular weights Mn (number average) of over 250, preferably over 600, with Kohlensäurebis-aryl esters at temperatures between 100 ° C and 200 ° C, preferably between 11O ⁰ C and 180 ° C, under vacuum below 35 Torr, preferably between 25 and 1 Torr, heated in the presence of catalysts, less than one mole of carbonic acid bis-aryl ester being used per OH group of the polyester diol and the hydroxyaryl compounds formed being distilled off.

P 2 712 435.2 also relates to aryl bis-carbonate of polyester diols extended over -OCOO groups.

Polyester polyols which are preferred according to P 2 712 435.2 (Le A 17 840) are polyester diols. Thus are the preferred item from P 2 712 435.2 (Le A 17 840) a method for

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-JIt

Production of bisaryl carbonates from extended carbonate groups Polyester diols and polyester diol bis-aryl carbonates extended via carbonate groups.

The polyesters containing hydroxyl groups according to P 2 712 435.2 (Le A 17 840) invention are, for example, reaction products of polyhydric, preferably dihydric and optionally additionally trihydric alcohols with polybasic, preferably dibasic, carboxylic acids. Instead of the free polycarboxylic acids, the corresponding Polycarboxylic anhydrides or corresponding polycarboxylic esters of lower alcohols or their Mixtures can be used to produce the polyester polyols. The polycarboxylic acids can be aliphatic, cycloaliphatic, aromatic and / or heterocyclic in nature and optionally substituted, for example by halogen atoms, 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, endomethylenetetrahydrophthalic anhydride, Glutaric anhydride, maleic acid, maleic anhydride, fumaric acid, dimeric and trimeric fatty acids such as oleic acid, optionally mixed with monomeric fatty acids. The polyhydric alcohols, optionally mixed with one another, e.g. ethylene glycol, propylene glycol- (1,2) and - (1,3), butylene glycol- (1,4) and - (2,3), hexanediol- (1,6), Octanediol (1,8), neopentyl glycol, cyclohexanedimethanol, (1,4-bis-hydroxymethyl-cyclohexane), 2-methyl-1,3-propanediol, Glycerine, trimethylolpropane, hexanetriol- (1,2,6), butanetriol- (1,2,4), Trimethylolethane, pentaerythritol, quinite, also thiodiglycol, diethylene glycol, triethylene glycol, tetra-

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ethylene glycol, polyethylene glycol, dipropylene glycol, polypropylene glycols, Dibutylene glycol and polybutylene glycols in question.

By choosing the defined excess of alcohol, the content of hydroxyl end groups and thus the "average" Molecular weight Mn specified. Preference is given to using polyesters made from aliphatic starting components.

Polyesters containing hydroxyl groups are, for example, by polymerization of a lactone, for example, such ^ - are prepared by condensing caprolactone or a hydroxycarboxylic acid, such as hydroxycaproic acid and a hydroxyl group-containing initiator. Mn is again obtained arithmetically as described above.

Those suitable for the method according to P 2 712 435.2 (Le A 17 840) Polyester polyols preferably have 2 to 4 hydroxyl groups, particularly preferably 2 hydroxyl groups

Carbonic acid bis aryl ester according to P 2 712 435.2 (Le A 17 840) are in particular those of the formula (I)

Ar-O-C-O-Ar, (I)

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

Particularly C.-C.-alkyls and also come as substituents Nitro, halogen, such as, for example, chlorine or bromine, are possible.

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Examples are diphenyl carbonate, alkyl substituted Diphenyl carbonates such as di-toluyl carbonates, halogen-substituted Diphenyl carbonates such as the di-chlorophenyl carbonate, dinaphthyl carbonate and alkyl-substituted ones and halogen-substituted dinaphthyl carbonates; here the nitro, alkyl or halogen substituents can be an both phenyl nuclei or on both naphthyl nuclei of the diaryl carbonates be the same or different or symmetrical or be asymmetrical to each other. For example, there are also phenyl toluyl carbonate, phenyl chlorophenyl carbonate, 2-toluyl-4-toluyl carbonate or 4-toluyl-4-chlorophenyl carbonate are suitable for the process.

Bis-aryl carbonates of over -OCOO groups Polyester diols according to P 2 712 435.2 (Le A 17 840) are therefore in particular those of the formula II

Ar-O-C

ti

0- (polyester) -0-CO-Ar, (II)

Ar has the meaning given above,

- (Polyester) - represents the divalent radical of one of the polyester diols described above and

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

Suitable catalysts for the process according to P 2 712 4 3 (Le A 17 840) are basic transesterification catalysts such as alkali or alkaline earth metal phenolates, alkali or Alkaline earth alcoholates and tertiary amines such as?

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■ Yes-

Triethylenediamine, morpholine, pyrrolidine, pyridine, triethylamine or metal compounds such as antimony trioxide, zinc chloride, Titanium tetrachloride and titanium acid 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.

These amounts of catalyst can, if appropriate, still fall below this level if the starting products do not contain any basic impurities when using the acidic catalysts, and contain no acidic impurities when using the basic catalysts. In interest The smallest possible amounts of catalyst are the smallest possible amounts of catalyst for the carbonic acid esters produced from polyester diols to have an inherent color that is as low as possible to prefer.

The process according to P 2 712 435.2 (Le A 17 840) is preferably carried out in substance, that is in the absence of
Solvent. If necessary, however, also under the
Reaction conditions inert solvents such as aliphatic
Hydrocarbons or aromatic hydrocarbons,
which may contain nitro groups, for example, can be used.

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

In the process according to P 2 712 435.2 (Le A 17 840)
Hydroxyaryl compounds formed can after completion

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■ to-

Reaction can be removed by using a batch process the hydroxyaryl compounds are separated off by distillation during the reaction. One carries out the transesterification reaction by a continuous procedure, then the hydroxyaryl compounds are by a fractional distillation separated from the reaction mixture.

According to a particularly preferred embodiment of the process according to P 2 712 435.2 (Le A 17 840), sodium phenolate is used reacted as a catalyst in a mixture of polyester diol and carbonic acid bis-aryl ester at 110 C and 150 ° C, less than one mole of carbonic acid bis-aryl ester is used per OH group of the polyester diol.

According to the process according to P 2 712 435.2 (Le A 17 840), bis-carbonic acid monoaryl esters can be extended by bridges via -OCOO Polyester diols are represented; surprisingly it was found 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 molecular non-uniformity of the starting polyester diols during the extension under simultaneous Esterification remains practically unchanged.

In the process according to P 2 712 435.2 (Le A 17 840), the desired molecular weight Mn is extended and esterified Polyesterdiols (II) by the amount of the diaryl carbonate reacted with the polyesterdiol (I) determined; it is generally true that η moles of polyester diol must be reacted with (n + 1) moles (I) in order to an η-fold, over -OCOO groups-extended polyester diol to arrive with terminal aryl carbonate groups (n has the values given in formula II).

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Λ \ -

The average molecular weights listed in the following examples are number average Mn, the osmometric unless otherwise stated.

The Staudinger index CVlm-av given was measured in THF at 25 ° C. and is given in -. For a definition of the Staudinger Index, see: HGElias: "Makromolekule", Hüthig & Wepf-Verlag, Basel, p. 265.

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Examples from P 2 712 435.2 (Le A 17 840)

1. 800 parts by weight of a polyester diol made from hexane-1,6-diol and adipic acid with an average molecular weight of Mn = 800 (determined from 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 6 Torr 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, the remaining traces of phenol can then be separated off in a thin-film evaporator at 190 C / 0.1 Torr. A colorless, viscous oil with an average molecular weight Mn of 1820 is obtained. The OH number is zero; the Staudinger index [ £ -7 _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 Mn = 20OO (determined from OH number measurement). 321 parts by weight of diphenyl carbonate and 0.12 parts by weight of sodium phenolate are added with stirring, nitrogen and a vacuum of 3 Torr for 2.5 hours

110 ° C, 2 hours at 130 ° C and 2.5 hours at 160 ° C. During this time, phenol is distilled off from the reaction mixture. If desired, the remaining traces of phenol can then be separated off in a thin-film evaporator at 110 ° C./0.1 torr. A colorless, viscous oil with an average molecular weight Mn of 4240 and a Staudinger index £ /> J 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 / neopentylglycol im molar ratio 65/35 of the average molecular weight

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-Vb-

Mn 2000 (determined by OH number measurement) 321 parts by weight Diphenyl carbonate and 0.12 part by weight of sodium phenolate are stirred, nitrogen and a vacuum of 2 Torr 2.5 hours at 110 ° C, 3 hours at 140 ° C and 3 hours heated at 150 ° C. During this time, the reaction mixture becomes Phenol distilled off. If desired, the remaining traces of phenol can then be added at 190 C / 0.1 Torr can be separated in a thin film evaporator. A colorless, viscous oil is obtained, which after some time solidified to a wax and has an average molecular weight Mn of 4240. The Staudinger Index is 0.25 and the OH number is zero.

4. 20OO parts by weight of a polyester diol made from adipic acid and a mixture of hexane-1,6-diol / neopentyl glycol in a molar ratio of 65/3 5 with an average molecular weight of Mn 2000 (determined by measuring the OH number). 285 parts by weight of diphenyl carbonate and 0.12 parts by weight of sodium are heated with stirring, nitrogen and a vacuum of 2 torr for 4 hours at 11O ⁰ 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, remaining traces of phenol can then be separated off in a thin-film evaporator at 190 ° C./0.1 Torr. A colorless wax with an average molecular weight Mn of 6270 is obtained. The Staudinger index Ct ⁷ J _thf is 0.32 and the OH number is zero.

5. 20OO parts by weight of a polyester diol from adipic acid and a mixture of hexane-1,6-diol / neopentyl glycol in molar ratio 65/35 of the average molecular weight Mn 2000 (determined by OH number measurement), 267.5 parts by weight

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2726Α17

Diphenyl carbonate and 0.12 part by weight of sodium phenolate are heated with stirring, nitrogen and a vacuum of 1 Torr for 3 hours at 110 ° C, 5 hours at 140 ° C, 2 hours at 150 ° C and 1 hour at 165 ° C. During this time, phenol is distilled off from the reaction mixture. If desired, remaining traces of phenol can then be separated off in a thin-film evaporator at 190 ° C./0.1 Torr. A colorless wax with an average molecular weight of Mn 8290 is obtained. The Staudinger index C? / Jtn-av> is 0.40 and the OH number is zero.

For the production according to the invention of those lengthened via carbonate groups Polyesterdiol-bis-diphenol-carbonate suitable diphenols are:

Hydroquinone
Resorcinol

Dihydroxydiphenyls
Bis (hydroxyphenyl) alkanes
Bis (hydroxyphenyl) cycloalkanes
Bis (hydroxyphenyl) sulfides
Bis (hydroxyphenyl) ether
Bis (hydroxyphenyl) ketones
Bis (hydroxyphenyl) sulfoxides
Bis (hydroxyphenyl) sulfones
-L, X ^ bis (hydroxyphenyl) diisopropylbenzenes

and their ring-alkylated and ring-halogenated compounds. These and other suitable aromatic dihydroxy compounds are e.g. in U.S. Patents 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 the German Offenlegungsschrift 2,063,050, 2,211,957.

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7726417

Suitable diphenols are, for example, bis (4-hydroxyphenyl) methane 4,4'-dihydroxydiphenyl

2,4-bis- (4-hydroxyphenyl) -2-methylbutane <±, J -.- Bi.s- (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) -propi.n and

2,2-bis (3,5-dibromo-4-hydroxyphenyl) propane.

Those which are suitable according to the invention and which are extended via carbonate groups Diphenols can be used either alone or in groups.

Polyester diol bis-diphenol carbonates according to the invention which have been extended via carbonate groups are for example those of the formulas IVa-IVh:

• 0- (polyester) -0-C

CH, CH,

CH ₃ CH ₃

o-C-0- (polyester)

.0-C-

dd

—O-c-

^ 3 «2

CH,

_{lVc

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-V

Cl

CH

Cl

* \ Vd-rvo-c.

Cl
I'.r

CH

qi -c σ;

CH

CH

O- (polyester JLq-c-

Cl

'Cl

? 3

-C

Cl

-OH (IVd)

Dr

-O-C-

O- (polyester) -D-CO

Br O -

Cl Mr

CH,

-O-C

O (polyester) -o-C-

Oi

0- (Polye3ter) _o-c-.

CH.

CH.

!! Ve)

IVf]

IVg)

O- (polyester) -O-C

Il

-OH

:NS)

in which - (polyester) - is the divalent radical in the formulas IVa of the polyester diols described on page 8-9.

- NS

Those according to the invention extended via carbonate groups Polyester diol bis diphenol carbonates can be used as starting bisphenols in the production of polycarbonates by the known two-phase boundary polycondensation process can be used. Polyester-polycarbonates of a specific structure are obtained in this way.

The process according to the invention for producing these polyester-polycarbonates is characterized in that the polyester-diol-bis-diphenol-carbonates according to the invention which have been extended via carbonate groups, in particular those of the formula IV _r

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with other diphenols, especially with those of the formula III, and with phosgene according to the two-phase boundary polycondensation process known for polycarbonate production at pH values between 9 and 14 and temperatures between 0 C and 80 C, preferably between 15 C and 40 C. 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 have two different, spatially separated phases, i.e. areas which are composed of a continuous amorphous polyester phase and a crystalline or amorphous crystalline 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 (Le A 18 01 9 additional advantages, such as an even better phase separation leading to better application properties of the corresponding polyester-polycarbonates leads.

The polyester-polycarbonates according to the invention have due Their multiphase structure has better heat resistance than comparable single-phase polyester-polycarbonates.

Single phase polyester-polycarbonates are described, for example, in U.S. Patent 3,151,615. You are after

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different processes available, but preferably after the "Pyiidinverl." ears.

The production of two phase polymeions, for example of polycarbonate-polycaprolaetonone, has so far only been possible by means of bischloroformic acid esters of polycaprolactones and polycaibonate oligomers (see French patent specification 2 235 9 () ^r j).

The same applies to the; although not as two-phase designated polyester-polycarbonates of DT-AS 1 162 559.

The use according to the invention of the carbonate groups-extended according to the invention Polyesterdiol-bis-diphenol-carbonate has the advantage over the use of corresponding bischloroformic acid esters that it is insensitive to hydrolysis and thus better shelf life and clearly bifunctional reactivity.

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

The different phases of the polyester according to the invention can be recognized with the help of di erenti al thermal analysis, the polyester phase, for example, having a freezing temperature of 70 ° C, the amorphous portion in the polycaibonate phase a glass transition temperature between 100 C and 15O C, and has the crystalline fraction dei PoIycarbonatphase has a Kristal1itschmelzpunkt between 170 ⁰ C and 2T) O ⁰ C.

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The high-molecular, segmented, thermoplastically processable polyester-polycarbonates, produced by the process according to the invention, show, in addition to the special thermal resistance, good transparency, highly elastic behavior and excellent elongation at break of τ 400%.

The other diphenols suitable for the production according to the invention of the polyester-polycarbonates from the polyester-diol-bis-diphenol carbonates according to the invention are those already for the production of the polyester-diol-bis-diphenol carbonates on pages 16-17 of these Patent application mentioned, in particular that of the formula III from page 4 of this patent application; 4,4'-dihydroxydiphenyl, for example, are suitable
Bis (4-hydroxyphenyl) methane
2,4-bis- (4-hydroxyphenyl) -2-methylbutane .L ·, .i_-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 of 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 are used. Any mixtures of these can also be used other diphenols can be used.

By incorporating small amounts of tri- or more than trifunctional compounds, especially those with three or more than three phenolic hydroxyl groups,

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/ 726417

preferably between 0.05-2 mol% (based on the diphenols used), branched products are also obtained better flow behavior during processing.

Examples of suitable tri- or more than trifunctional compounds are:

Phloroglucinol, 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- ^ l, 4- (4 , 4'-dihydroxydiphenyljcyclohexyiy-propane, 2,4-bis- (4-hydroxyphenyl-isopropyl) -phenol, 2,6-bis- (2'-hydroxy-5'-methylbenzyl) -4-methyl-phenol, 2, 4-dihydroxybenzoic acid, 2- (4-hydroxyphenyl) -2- (2,4-d! Hydroxyphenyl) -propane, 1,4-bis- (4,4 "-dihydroxytriphenyl-methyl) -benzene and 3,3-bis - (4-hyaroxyphenyl) -2-oxo-2,3-dihydroindole and 3,3-bis- (3-methyl-4-hydroxyphenyl) -2-oxo-2,3-dihydroindole.

The branching of the polyester-polycarbonates according to the invention can also take place via the polyester component, namely by mixing the carbonic acid aryl esters of polyester polyols with three or four aryl groups with the converts the above-mentioned di-, tri- and / or tetraphenols to corresponding polyester polyol poly-polyphenol carbonates according to the process of the present invention, and the polyphenols thus obtained in molar amounts of up to 50 mol%, based on the mol of polyester diol-bis-diphenol used carbonates, used in the polyester-polycarbonate synthesis according to the present invention.

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0 098 ^r »l / n272

? Ί Ί 6 4 Ί

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

The chain length of the polyester-polycarbonates can optionally be used for example by adding polyester mono-ol mono-diphenol carbonates polyester diol-bis-diphenol-carbonates used in molar amounts or on moles via carbonate groups, up to about 50 mol% can be adjusted.

The production according to the invention of the high molecular weight, segmented, thermoplastically processable polyester-polycarbonates takes place according to the two-phase boundary 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 polyester diol bis-diphenol carbonates according to the invention which have been extended via carbonate groups, in particular those of the formula IV, or their mixtures? dissolved in a water-immiscible inert organic solvent and added. Then, at a temperature between 0 ⁰ C and 80 C, preferably, b initiated C and 4O ° C and a pH between 9-14 phosgene. 1 After the phosgenation, the polycondensation takes place by adding 0.2-10 mol% of tertiary aliphatic amine, based on mol of diphenol. Here, times between 5 minutes and 90 minutes are required for the phosgenation, and times between 3 minutes and 3 hours for the polycondensation.

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The present invention thus relates to the production of polyester-polycarbonates, which is characterized in that the polyesterdiol-bis-diphenol-carbonates according to the invention, especially those of the formula IV, which have been extended via carbonate groups, with other diphenols, especially those of the formula III, and with phosgene in a liquid mixture of inert organic solvent and alkaline aqueous solution at temperatures between O ⁰ C and 80 ⁰ C, preferably between 15 ° C and 40 ° C, at a pH between 9 and 14, and after the addition of phosgene by adding 0.2 mol% to 10 mol%, based on the molar amount of diphenol, polycondensed, the weight ratio of polyester diol-bis-diphenol carbonate extended by carbonate groups to other diphenol of the polycarbonate and the polyester the polyester-polycarbote is determined.

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

The resulting solutions of the polyester-polycarbonates in the organic solvents are analogous to the solutions of processed thermoplastic polycarbonates produced by the two-phase interface process, the Polyester-polycarbonates can also be post-treated, and either will

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 let or

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b) during isolation, for example in a venting extruder already subjected to shear forces, or

c) prior to isolation in the manufacture of polyester-polycarbonates allow solvent used by the two-phase interface process to gel.

As an inert organic solvent for the inventive Manufacturing processes for 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 of these Solvents suitable.

_{Solutions of Li (OH) 2} , 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.

As tertiary aliphatic amines for the inventive Processes are those with 3 to 15 carbon atoms suitable, So 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 in each case on the total amount of diphenols used (= respective sum of carbonate groups-extended Polyester diol bis diphenol carbonates and others Diphenols).

Those produced by the process of the invention Polyester-polycarbonates can be isolated using the following methods:

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a. By distilling off the organic solvent up to a certain concentration, with a high percentage (about 30-40% by weight) polymer solution is obtained, with the subsequent slow evaporation the remaining solvent gels the polyester-polycarbonate.

b. By precipitating 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 about 160-240 C under the conditions known for polycarbonate extrusion and using shear forces.

The gelation of the process according to the invention produced polyester-polycarbonates, be it without isolation in the processed organic phase of the Two-phase reaction mixture or in a separate solution of the previously isolated polyester-polycarbonates in organic Solvents, takes place by cooling the high-percentage 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 are required.

The gelled product can be worked up to form a powder grain mixture be, the obtained polyester-polycarbonate

ο ο

48 hours at 50 ° C. and 24 hours at 100 ° C. in vacuo is dried.

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■ l> s

2726Λ17

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

The heat treatment of the isolated polyester-polycarbonates takes place between 5 minutes and 24 hours at temperatures between 40 ° C and 170 ° C.

The action of shear forces on the insulated polyester-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 of 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 inventive implementation of the invention over Carbonate group-extended polyester diol bis-diphenol carbonates with diphenols and with phosgene according to the two-phase interface process is done quantitatively; thus the respective reactant ratio is determined by over Carbonate groups-extended polyester-diol-bis-diphenol carbonate to other diphenol from the polycarbonate component and the polyester component of the polyester-polycarbonates to be synthesized in each case.

The proportion of polycarbonate in the process according to the invention produced polyester-polycarbonates is, depending on the desired property profile, approximately between 3 5 and 80 % By weight, the hardness and heat resistance increasing as the proportion of polycarbonate increases, and the elasticity and Elongation at break decreases.

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As the polycarbonate portion of the polyester-polycarbonates according to the invention is the amount by weight of aromatic polycarbonate structural units represented by Formula V below

(V)

where D stands for the diphenolate residues in the polyester-polycarbonate is to be understood in particular on aromatic polycarbonate structural units of the formula IHa

where X and
to have.

(Ilia)

F = * * - ^ O

_l3 Y ₂

to Y. the meaning given for formula III

As the polyester component of the polyester-polycarbonates according to the invention is accordingly the amount by weight of carbonate group-extended polyester diolate block units one of the on p. 7 - 9 described polyester diols of the simplified formula VI

-O- (polyester) -0-C-

Il

0 y

(VI)

to be understood where η is an integer from 2 to 20, preferably 2 to 10 means.

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The present invention thus also relates to polyester polycarbonates, which are characterized in that they are about 30 to 95 wt .-%, preferably about 35 to 80% by weight, of aromatic polycarbonate structural units of the formula V, in particular those of the formula IHa, and about from 70 to 5% by weight, preferably from about 65 to 20% by weight, of polyester diolate block units extended via carbonate groups the simplified formula VI exist.

Polyester-polycarbonates according to the invention are for example those which contain from 30 to 95% by weight, preferably from 35 to 80% by weight, of polycarbonate structural units Formula IIIb pass,

where Y

(HIb)

Is H, Cl, Br or CH, and from 70 to 5% by weight, preferably 65 to 20% by weight, of carbonate groups-extended Polyesterdiolate block units exist.

The polyester-polycarbonates according to the invention should have average molecular weights Mw (weight average) of 25,000 to 25ΟΟΟΟ, preferably 40,000 to 150,000, determined by the light scattering method with a light scattering photometer. The relative solution viscosities Φ (measured on 0.5 g in 100 ml of CH ₂ Cl ₂ 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.

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The high molecular weight prepared by the process of this invention, segmented, thermoplastically processable polyester-polycarbonates are characterized in that, as measured by differential thermal analysis of the polyester content amorphous present and a glass transition temperature between -100 C and +100 C, preferably between -80 C and +20 ⁰ C. , and that the polycarbonate portion is partially crystalline with a crystalline 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 above 80 ° C., preferably above 100 ° C.

This differentiation of the glass transition temperature of the polyester component of the freezing temperature and the crystalline melting temperature of the polycarbonate component is characteristic for a phase separation of polyester and polycarbonate components.

The partial crystallinity, detectable by a measurable enthalpy of fusion of the polycarbonate portion of the invention Polyester-polycarbonate which is at least 1-8 cal / g polymer can be prepared by stretching and by the aforementioned Subsequent tempering (5 minutes to 25 hours) at 40 170 C or by the aforementioned action of shear forces can be increased by 50% during thermoplastic processing in a multi-screw extruder, whereby the heat resistance of products increases, the appearance changes from transparent to opaque to non-transparent.

The partially crystalline elastic polyester-polycarbonates can each be below or in the range of the crystallite melting point of the crystalline polycarbonate content

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Temperatures from 130 ° C to max. 2 50 C processed thermoplastically , whereby a substantial proportion of the crystallinity is not lost. At processing temperatures above of the crystalline melting point of the crystalline polycarbonate component, amorphous, transparent products are obtained.

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

The work-up and isolation according to the invention takes place of the polyester-polycarbonates without heat treatment, without gelling and without the action of shear forces, single-phase ones are obtained Polyester-polycarbonates, i.e. products with only one freezing temperature that can be measured by means of differential thermal analysis .

The UV stability and hydrolysis stability of the polyester-polycarbonates according to the invention can be improved by amounts of UV stabilizers customary for thermoplastic polycarbonates, such as substituted ones "Benzophenones" or "Benztriazoles", by hydrolysis inhibitors, such as mono- and especially polycarbodiimides, (see 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 Polyester-polycarbonates, and through in the chemistry of thermoplastic polyesters and thermoplastic polycarbonates known anti-aging agents.

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To modify the products according to the invention, substances such as carbon black, kieselguhr, kaolin, clays, CaF ₂ , CaCO ₃ , aluminum oxides and customary glass fibers in amounts of 2 to 40 wt Fillers as well as nucleating agents can be added.

If flame-resistant products are required, approx. 5 to 15% by weight, based in each case on the weight of the polyester-polycarbonate, known in the chemistry of thermoplastic polyesters and thermoplastic polycarbonates Flame retardants such as antimony trioxide, tetrabromophthalic anhydride, Hexabromocyclododecane, tetrachlor or tetrabromobisphenol-A or tris (2,3-dichloropropyl) phosphate are admixed, the polycarbonate fractions of the polycarbonates according to the invention being random built-in tetrachloro- and tetrabromobisphenols also show flame-retardant properties.

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

The polyester-polycarbonates obtained by the process according to the invention can advantageously be used anywhere can be used where a combination of hardness and elasticity, especially low-temperature flexibility, is desired is, e.g. in the body shop, for the production of low-pressure tires for vehicles, for the sheathing of hoses, Plates, tubes and for flexible drive pulleys.

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-W-

The ones listed in the following examples: i middle Molecular weights are number average Mn and determined by determining the OH number.

The Staudinger index given in Example A was measured in THF at 25 ° C. and indicated in -.

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

P. 265.

The relative solution viscosity ρ of Examples C ₁ -C is defined by the viscosity of 0.5 g of polyester-polycarbonate in 100 ml of methylene chloride at 25 C.

The tear strength and elongation at break were measured in accordance with DIN 53 and 53 457, respectively.

Gel chromatographic investigations were carried out in tetrahydrofuran with Styragel columns (separation range 1.5 χ 10 8, 1 χ A, 3 χ 10 A and 2 χ 10 A) carried out at room temperature.

The calibration of bisphenol A polycarbonate was used for the determination. No major deviations were found in comparison with the Mw determination using the light scattering method.

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

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Example A.

-Hv

Production of a carbonate group-extended polyester diol bis-phenyl carbonate

2OOO parts by weight of a polyester diol made from adipic acid and a mixture of hexane-1,6-diol / neopentyl glycol in a molar ratio of 65/35 with an average molecular weight of Mn 2000 (determined by measuring the OH number). 285 parts by weight of diphenyl carbonate and 0.12 part by weight of sodium phenolate are heated for 4 hours at 110 ° C., 3 hours at 140 ° C. and 5 hours at 155 ° C. with stirring, nitrogen and a vacuum of 2 Torr. During this time, phenol is distilled off from the reaction mixture. If desired, remaining traces of phenol can then be separated off in a thin-film evaporator at 190 ° C./0.1 Torr. A colorless wax with an average molecular weight Mn of 6270 is obtained. The S tauding index / TnJwo is 0.32 and

C- I Hf

the OH number is zero.
Example B 1

Production of a carbonate group-extended polyesteidiol bis (bisphenol A) carbonate, which still contains 2.6% by weight of bisphenol A.

313.5 parts by weight of bisphenyl carbonate of a carbonate group-extended one Polyester diols made from adipic acid and a mixture of 1,6-hexanediol and neopentyl glycol in the molar range Ratio 65/35 of the average molecular weight M 6270, and that 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 bis-

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phenol A to bisphenol A = 1: 100) with stirring and nitrogen atmosphere initially for 1 hour at 125 ° C, then Heated for 4 hours at 150 ° C. and 0.05 torr. During this 8.1 parts by weight of phenol are distilled off. A colorless wax is obtained.

Example B 2

Production 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 of a polyester diol elongated via carbonate groups and made from adipic acid and a mixture of 1,6-hexanediol / neopentyl glycol in a molar ratio of 65/3 5 with an average molecular weight of Mn 4,240, and which was prepared according to Example A, 41 , 5 parts by weight of 2,2-bis- (4-hydroxyphenyl) -propane (bisphenol A) and 0.1 part by weight of sodium phenolate are initially stirred and under a nitrogen atmosphere for 1 hour at 125.degree. C., then for 4 hours at 150.degree ⁰ C and 0.8 torr heated. 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 still contains 2,2-bis- (3, 5-dimethyi-4-hydroxyphenyl) propane in amounts of Contains 4.6% by weight

297 parts by weight Bisphenyl carbonate one extended by carbonate groups Polyester diols made from adipic acid and a mixture of 1,6-hexanediol / neopentyl glycol in a molar ratio

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ratio 65/35 of the average molecular weight Mn 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 (sodium bisphenolate of bisphenol A: bisphenol A = 1: 100) are added with stirring under a nitrogen atmosphere First heated for 1 hour at 125 ° C., then for 5 hours at 150 ° C. and 0.2 torr. During this time will be 9.8 parts by weight of phenol distilled off.

Example B 4

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 contains in amounts of 3.1 wt .-%

313.5 parts by weight of bisphenyl carbonate of a carbonate group-extended Polyester diols made from adipic acid and a mixture of 1,6-hexanediol / neopentyl glycol in the molar range Ratio 65/35 of the average molecular weight Mn 6270, and that was prepared according to Example A, 37% by weight of 2,2-bis- (3,5-dimethyl-4-hydroxyphenyl) propane and 0.19 parts by weight Catalyst (sodium bisphenolate of bisphenol A: bisphenol A = 1: 100) are initially activated with stirring and nitrogen atmosphere Heated for 1 hour at 125 ° C., then 5.5 hours at 150 ° C. and 0.2 torr. During this time, 7.4 parts by weight Phenol distilled off.

Example C 1

Production of a polyester-polycarbonate with 50% by weight of polyester

110.6% by weight of this viscous oil from Example B1, dissolved

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■ MS

in 1725 parts by weight Methylene chloride, become a solution of 80 wt. -Tl. 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. Given water. Within 30 minutes, 58.3 parts by weight are added at 20-25 ° C. with stirring and under a nitrogen atmosphere. Phosgene initiated. During the introduction, 126 parts by weight are added at the same time. 45 percent NaOH is added dropwise in such a way that the pH value remains constant at pH 13. After the phosgene has been introduced, 39.8 parts by weight are added. a 1 percent Triethylamine solution was added and the mixture was stirred for 1 hour. The organic phase is separated off, successively with 2 percent phosphoric acid and finally with distilled water. Washed water until electrolyte-free. After the water has been separated off, the organic phase can be worked up using the following methods:

C.1.1 By distilling off the CH-Cl- up 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 gels the polyester-polycarbonate and can be worked up further to form a powder-grain mixture. The polyester-polycarbonate obtained is dried for 48 hours at 50.degree. C. and 24 hours at 100.degree. C. in a vacuum.

C.1.2 By distilling off the solvent, drying in Vacuum drying cabinet at about 80-110 ° C and 15 Torr and then Grinding gives a finely divided solid product.

C.1.3 By precipitating the polyester-polycarbonate from the organic Phase with, for example, methanol, ethanol, isopropanol, acetone, aliphatic hydrocarbons and

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cycloaliphatic hydrocarbons and subsequent drying in a vacuum drying cabinet at 80-11O ⁰ C and 15 Torr.

C.1.4 By concentrating the organic phase in the evaporation extruder and subsequent extrusion at about 160-24O ⁰ C under the conditions known for polycarbonate extrusion.

The rel. The viscosity of the polyester-polycarbonate obtained according to C.1.1 - C.1.4 is f ^ rel = 1.63 (measured in CH ₂ Cl ₂ 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 transition temperature (glass transition temperature) of the polyester component of -38 C, a glass transition temperature (Glass transition temperature) of the amorphous polycarbonate portion of 120C and a crystallite melting point of the crystalline polycarbonate portion 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

Manufacture of a carbonate group-extended polyester-polycarbonate with 50% by weight polyester

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115.1 parts by weight of the viscous oil from Example B 2, dissolved in 1725 parts by weight. Methylene chloride are added to 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 caustic soda.

For this purpose, a solution of 0.52 parts by weight is added. 1,4-bis (4 ', 4 "-dihydroxytriphenylmethyl) benzene and 45 parts by weight 5 percent Caustic soda added.

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

The rel. Viscosity of the polyester-polycarbonate is

^CH 2 ^C1 2 ⁾

According to gel chromatographic determination, the polymer shows a maximum at 45,000 and a secondary maximum at 200,000.

The mechan. Properties of one cast from methylene chloride Film with 50% by weight polyester and 50% by weight polycarbonate

Tear strength: 20.1 MPA

Elongation at break: 4 26%

The granulated polyester-polycarbonate shows after differential thermal analysis a glass transition temperature (glass transition temperature) of the polyester component of -34 ° C, a glass transition

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transition temperature (glass transition temperature) of the amorphous polycarbonate component of 125 C and a crystalline melting point of the crystalline polycarbonate portion of approx. 185 C. The The enthalpy of fusion of the crystalline polycarbonate component is between 2.5 and 5.5 cal / g polymer.

Example C 3

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 mol% per mol of bisphenol units), dissolved in 1725 parts by weight Methylene chloride, become a solution of 73.5 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 given distilled water.

Within 30 min. With stirring under a nitrogen atmosphere 95.6 parts by weight Phosgene introduced while at the same time 225 parts by weight. 45 percent Caustic soda to keep things constant of pH 13 are added dropwise. After the phosgene has been introduced, 5.4 parts by weight are added for complete condensation. Tributylamine (= 9 mol% per mol of bisphenol units) were added. The approach becomes more viscous. After 3 hours, the organic ones are separated Phase off and the polyester-polycarbonate is recovered as described in Example C 1 (work-up C 1.1).

The rel. The viscosity of the polyester-polycarbonate is <£ _rel = 1.55 (in CH ₂ Cl ₂ ).

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Example C 4

-Ma-

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 mol% per mol 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 min with stirring and nitrogen atmosphere 95.6 parts by weight Phosgene introduced while at the same time 235 parts by weight. 45 percent Caustic soda be added dropwise to keep pH 13 constant. After the phosgene has been introduced, condensation takes place completely 5.4 parts by weight Tributylamine (= 9 mol% per mol of bisphenol units) was added. The approach becomes more viscous. To The organic phase is separated off for 3 hours and the polyester-polycarbonate is recovered as in Example C 1 (work-up C 1.1) described.

The rel. The viscosity of the polyester-polycarbonate is V £ rel = ^{1 '68}

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ORIGINAL INSPECTED

Claims (21)

Claims . ^, Process for the preparation of carbonate groups elongated Polyester diol bis diphenol carbonates, characterized in that one polyester polyols with molecular weights Mn (number average) over 250, with Carbonic acid bis aryl esters at temperatures between 100 ° C and 200 ° C in a vacuum below 35 Torr in the presence heated by catalysts, with less than 1 mol of carbonic acid bis-aryl ester per OH group of the polyester polyol are used and the resulting hydroxyaryl compound is distilled off, and the obtained via carbonate groups-extended polyester diol bis-aryl carbonates heated with diphenols at temperatures between 100 and 200 C in a vacuum below 35 Torr in the presence of catalysts, wherein for a carbonic acid aryl ester group of the polyester diol bis-aryl carbonate extended via carbonate groups more than 1 mol of diphenol can be used and the hydroxyaryl compound formed is distilled off. 2. The method according to claim 1, characterized in that the obtained carbonate groups-extended Polyesterdiol-bis-arylcarbonate along with excess Reacts carbonic acid bis aryl ester with 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 formula IV Le A 18 034 - 42 809851/0272 ORIGINAL INSPECTED 27264 Γ / -OC- O (polyester) -OC- O Il wherein
-(Polyester) the divalent radical of the reaction product of one or more dihydric alcohols with one or more dibasic carboxylic acids is to be understood as an integer from 2 to 20, preferably 2 to 10, means -CH ₂ -, CH ₃ , -C- , O, S or SO ₂ and Y ₁ and Y ₄ are identical or different and are hydrogen or halogen, obtained according to processes of claim 1. 5. Carbonate group-extended polyester diol bis-diphenol carbonates of formula IVa -O- C- [O (polyester) -O-C Il O O -OH wherein η and - (polyester) - the meaning given in claim 4 to have. Le A 18 034 - 43 - 809851/0272 6. Carbonate group-extended polyester diol bis-diphenol carbonates of formula IVb -O-C • O- (polyester) -O-C • O- < Il Il ⁰ ° n wherein η and - (polyester) - the meaning given in claim 4 to have. 7. Carbonate group-extended polyester diol bis-diphenol carbonates of formula IVc CH ₃ CH ₃ : ■ O- (polyester) -O-C CH ₃ CH ₃ wherein η and - (polyester) - the meaning given in claim 4 to have. 8. Carbonate group-extended polyester diol bis-diphenol carbonates of formula IVd CH ₃ he ' ^N \ -C-fM -OC- O- (polyester) -0-C- 0 - {^ CH ₃ CH -OH, wherein η and - (polyester) - the meaning given in claim 4 to have. Le A 18 034 - 44 809851/0272 9. Carbonate group-extended polyester diol bis-diphenol carbonate of formula IVe Br F% CH 3 ^ Br -V V-OC- O (polyester) -OC ^Br CH ^Br Br wherein η and - (polyester) - the meaning given in claim 4 to have. 10. Carbonate group-extended polyester diol bis-diphenol carbonates of formula IVf CH -O-C-Io (polyester) -OC wherein η and - (polyester) - have the meaning given in claim 4. 11. Carbonate group-extended polyester diol bis-diphenol carbonate of the formula IVg CH- CH-, Ö O (polyester) -0-C tr CH -OH Le A 18 034 - 45 - 809851/0272 wherein η and - (polyester) - the Be mentioned in claim 4 have meaning. 12. Carbonate group-extended polyester diol bis-diphenol carbonates of formula IVh O (polyester) -0-C O - ('_ -SC ^X ) -OC- Jn before in η and - (polyester) - the meaning given in claim 4 to have. 13. Use of the carbonate groups-extended polyester diol bis-diphenol carbonates of claims 3 to 12 for the production of polyester-polycarbonates. 14. Use of the product mixture obtained according to claim 2 for the production of polyester-polycarbonates. 15. Process for the production of polyester-polycarbonates, characterized in that the carbonate groups are lengthened Polyester diol bis diphenol carbonates of the claims 3 to 12, with other diphenols and with phosgene in a liquid mixture of inert organic Solvent and alkaline aqueous solution at temperatures between 0 C and 80 C at a pH between 9 and 14 reacted, and after the addition of phosgene by adding 0.2 mol% to 10 mol% based on the molar amount of diphenol, polycondensed, the weight ratio of polyester lengthened by carbonate groups Le A 18 034 - 46 - 809851/0272 diol-bis-diphenol-carbonate to other diphenol from dem Polycarbonate content and the polyester content of the polyester-polycarbonates is determined. 16. The method according to claim 15, characterized in, that as other diphenols those of the formula III are implemented in which -CH--, CH ₃ ,, 0, S or SO- and -C- CH ₃ - to Y. are identical or different and are hydrogen or halogen. 17. Polyester-polycarbonates obtained according to claims 15 to 18. Polyester-polycarbonates, characterized in that they consist of about 30 to 95% by weight of aromatic polycarbonate structural units the formula IHa Le A 18 034 - 47 - 809851/0272 wherein X and Y ₁ to Y ₄ have the meaning given in claim 17 and about 70 to 5 wt .-% via carbonate groups-elongated polyester diolate block units of the simplified Formula VI 0- (polyester) ■ 1 -0-CJ _n consist of what
η an integer from 2 to 20, preferably 2 to 10, is. 19. Polyester-polycarbonates according to claim 17, characterized in that that they consist of about 35 to 80% by weight of structural units of the formula IVa and about 65 to 20% by weight of polyester diolate block units of the simplified formula VI extended via carbonate groups -0- (polyester) -C-O- " 1 C-O- l ⁿ exist. 20. Polyester-polycarbonates according to claims 18 and 19, characterized in that the aromatic polycarbonate structural units correspond to the formula IHb Le A 18 034 - 48 - 809851/0272 ■% - wherein Y is H, Cl, Br or CH ₃ . 21. Process for the thermoplastic processing of polyester-polycarbonates of claims 17 and 20, characterized in that thermoplastic processing below or in the area of the crystallite melting point of the crystalline polycarbonate content at temperatures between 130 and 250 C. Le A 18 034 - 49 - 809851/0272