DD287480A5 - PROCESS FOR THE PREPARATION OF DIHYDROXYDIPHENYLCYCLOALKANES AND THEIR USE - Google Patents

Abstract

The invention relates to processes for the preparation of Dihydroxydiphenylcycloalkanen of the formula * wherein the substituents R1 to R4, X and m have the meaning given in the description, and their use for the preparation of high molecular weight polycarbonates. According to the invention, the compounds of the formula I are prepared by known processes. Formula (I) {Dihydroxydiphenylcycloalkane Preparation; Use; Polycarbonates, high molecular weight}

Description

(V)

wherein

R ¹ and R ^{2 have} the meaning given for formula (I), with ketones of formula (Vl)

O Il

(Vl)

wherein

X, m, R ³ and R ^{4 have} the meaning given for formula (I), in the molar ratio (V) :( VI) between 2: 1 and 10: 1, preferably between 2.5: 1 and 6: 1 at temperatures between -30 ⁰ C and 300 ⁰ C, preferably between -15 ° C and 150 ⁰ C and at pressures of 1 to 20bar, preferably from 1 to 10bar in the presence of acidic catalysts and optionally in the presence of co-catalysts and / or solvents and / or dehydrating agents.

2. Use of the diphenols of the formula (I), characterized in that they are used for the preparation of high molecular weight, thermoplastic, aromatic polycarbonates.

Field of application of the invention

The invention relates to processes for the preparation of Dihydroxydiphenylcycloalkanen and their compound for the preparation of high molecular weight polycarbonates.

Characteristic of the known state of the art

For the preparation of high molecular weight polycarbonates suitable diphenols sindz. See, for example, U.S. Patent Nos. 3,028,365, 2,998,335, 3,148,172, 3,275,601, 2,912,337, 3,231,367, 3,006,278, and 2,999,846, German Laid-Open Patent Publications Nos. 1570703, 2063050, 2063052, 2110956, French Patent Specification No. 1561518 and the monograph "H. Schnell, Chemistry and Physics of Polycarbonates, Interscience Publishers, New York 1964 ".

Object of the invention

Through-the process of the invention Dihydroxydiphenylcycloalkane be provided, which are particularly suitable for the production of high molecular weight thermoplastic polycarbonates, which are characterized by high heat resistance in combination with a good other property pattern, are suitable.

Explanation of the essence of the invention

The present invention has for its object to provide processes for the preparation of Dihydroxydiphenylcycloalkanen available.

The present invention relates to processes for the preparation of dihydroxydiphenylcycloalkanes of the formula (I)

(D,

R ¹ and R ¹ independently of one another are hydrogen, halogen, preferably chlorine or bromine, C ¹ -C ₈ -alkyl, C ¹ -C ₆ -cycloalkyl,

C ₁ -C 10 -aryl, preferably phenyl, and C ₇ -C ₁ -j-aralkyl, preferably phenyl-C ₁ -C ₄ -alkyl, in particular benzyl, m is an integer from 4 to 7, preferably 4 or 5,

R ^{J and} R ^{4 are} individually selectable for each X, independently of one another are hydrogen or C 1 -C 6 -alkyl and X is carbon,

with the proviso that on at least one atom XR ³ and R ^{4 are} simultaneously alkyl.

X, R ³ and R ⁴ are preferably simultaneously alkyl at 1-2 atoms, in particular only at one atom. Preferred alkyl is methyl; the X atoms in the α-position to the di-phenyl-substituted C atom (C-1) are preferably not dialkyl-substituted, whereas alkyl disubstitution in the β-position to C-1 is preferred. It is particularly preferred that an X atom dialkylsubstituted in the β-position, and an X atom in the β'-position is monoalkyl-substituted.

In particular, the invention provides dihydroxydiphenylcycloalkanes having 5 and 6 ring C atoms in the cycloaliphatic radical (m = 4 or 5 in formula (I), such as, for example, the diphenols of the formulas

H ₃ C

-C-

(II)

^HCr "O

(III) and

(IV)

wherein the 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane (formula II) is particularly preferred.

The dihydroxydiphenylcycloalkanes of the formula (I) according to the invention can be prepared in a manner known per se by condensation of phenols of the formula (V)

and ketones of the formula (VI) O

in the formulas (V) and (VI) X, R ¹ , R ¹ , R ³ , R ⁴ and m have the meaning given for formula (I).

The phenols of formula (V) are either known from the literature or by literature methods (see, for example, for cresols and xylenols, Ullmann's Encyclopedia of Industrial Chemistry 4, revised and expanded edition Volume 15, pages 61-77, Verlag Chemie-Weinheim-New York 1978 ; technical chlorine phenols, Ullmann's Encyclopedia de ^r Chemie, 4th edition, Verlag Chemie, 1975, Volume 9, pages 573-582; and alkylphenols, Ullmann's Encyclopedia of Industrial Chemistry, 4.Aufldge, Verlag Chemie 1979, Volume 18, pages 191-214).

Examples of suitable phenols of the formula (V) are:

Phenol, o-cresol, m-cresol, 2,6-dimethylphenol, 2-chlorophenol, 3-chlorophenol, 2,6-dichlorophenol, 2-cyclohexylphenol, 2,6-diphenylphenol and o-benzylphenol.

The ketones of the formula (VI) are known from the literature (see, for example, Beilstein's Handbuch der Organischen Chemie, 7th volume,

4th edition, Springer-Verlag, Berlin, 1925 and the corresponding supplementary volumes 1 to 4, and J. Am. Chem. Soc. VoI 79 [1957], pages 1488-1492, U.S. Patent 2692289, Allen et al., J. Chem. Soc., [1959] 2186-2192, and J. Org. Chem. Vol.38, [1973], pp 4431-4435, J. Am. Chem. Soc. 87, [1965], pages 1353-1364).

A general method for the preparation of ketones of the formula (VI) is described, for example, in "Organikum, 15th edition, 1977, VEB Deutscher Verlag der Wissenschaften, Berlin, for example, page 698.

Examples of known ketones of the formula (VI) are:

3,3-dimethylcyclopentanone, 3,3-dimethylcyclohexanone, 4,4-dimethylcyclohexanone, S-ethyl-S-methylcyclopentanone, 2,3,3-trimethylcyclopentanone, 3,3,4-trimethylcyclopentanone, 3,3-dimethylcycloheptanone, 4, 4-dimethylcycloheptanone, 3-ethyl-3-methylcyclohexanone, 4-ethyl-4-mothylcyclohexanone, 2,3,3-trimethylcyclohoxanone, 2,4,4-trimethylcyclohexanone, 3,3,4-trimethylcyclohexanone, 3,3,5- Trimethylcyclohexanone, 3,4,4-trimethylcyclohexanone, 2,3,3,4-tetramethylcyclopentanone, 3,3,5-trimethylcycloheptanone, 3,1,3-trimethylcycloheptanone, 5-ethyl-2,5-dimethylcycloheptanone, 2,3,3, 5-tetramethylcycloheptanone, 2,3,5,5-tetramethylcycloheptanone, 3,3,5,5-tetramethylcycloheptanone, 4-ethyl-2,3,4-trimethylcyclopentanone, 3-ethyl-4-isopropyl-3-methyl-cyclopentanone, 4-sec. Butyl-S.S.-dimethylcyclopentanone, 2-isopropyl-3,3,4-trimethylcyclopentanone, S-ethyl-isopropyl-S-methylcyclohexanone, 4-ethyl-3-isopropyl-4-methylcyclohexanone, 3 sec.

Butyl ^ adimethylcyclohexanone, 2-butyl-3,3,4-trimethylcyclopentanone, 2-butyl-3,3,4-trimethylcyclohexanone, 4-butyl-3,3,5-trimethylcyclohexanone, S-isohexyl-S-methylcyclohexanone, and SSe -Trimethylcyclooctanon.

Examples of preferred ketones are

CH ₃ CH

and

For bisphenol preparation, generally 2 to 10 moles, preferably 2.5 to 6 moles of phenol (V) are used per mole of ketone (VI). Preferred reaction times are 1 to 100 hours. In general, one works at temperatures of -30 ° C to 300 ° C, preferably from -15 ⁰ C to 150 ° C and at pressures of 1 to 20 bar, preferably from 1 to 10 bar.

The condensation is generally carried out in the presence of acidic catalysts. Examples are hydrogen chloride, hydrogen bromide, hydrogen fluoride, Bortr ifluorid, aluminum trichloride, zinc dichloride, titanium tetrachloride, tin tetrachloride, phosphorus halides, phosphorus pentoxide, phosphoric acid, concentrated hydrochloric acid or sulfuric acid and mixtures of acetic acid and acetic anhydride. It is also possible to use acid longlacer.

Furthermore, the reaction by addition of co-catalysts such as C ^ C ^ alkyl mercaptans, hydrogen sulfide, thiophenols, thioacids and dialkyl sulfides preferably in amounts of 0.01-0.4 mol / mol of ketone, in particular 0.05-0.2MoI / Mole of ketone to be accelerated.

The condensation may be carried out without solvent or in the presence of an inert solvent (e.g., aliphatic and aromatic hydrocarbon, chlorinated hydrocarbon).

In cases where the catalyst acts as a dehydrating agent at the same time, it is not necessary to use additional dehydrating agents, but in order to obtain good conversions, the latter is in any case advantageous if the catalyst used does not bind the water of reaction.

Suitable dehydrating agents are, for example, acetic anhydride, zeolites, polyphosphoric acid and phosphorus pentoxide.

The present invention thus also provides a process for the preparation of the dihydroxydiphenylcycloakac of the formula (I)

R 'and R ² independently of one another are hydrogen, halogen, preferably chlorine or bromine, C ¹ -C 6 -alkyl, C 3 -C 6 -cycloalkyl,

C ₆ -C ₁₀ -alkyl, preferably phenyl, and C ₁ -C ₆ -alkyl, preferably phenyl-C 1 -C 4 -alkyl, in particular benzyl, m is an integer from 4 to 7, preferably 4 or 5,

R ³ and R ^{4 are} individually selectable for each X, independently of one another hydrogen or C ₍ C ₆ alkyl and X is carbon

with the proviso that on at least one atom XR ³ and R ^{4 are} simultaneously alkyl, which is characterized in that phenols of the formula (V)

(V)

R ¹ and R ^{2 have} the meaning given for formula (I), with ketones of formula (Vl)

(Vl)

X, m, R ³ and R ^{4 have} the meaning given for formula (I),

in the molar ratio (V) :( VI) of 2: 1 to 10: 1, preferably from 2.5: 1 to 6: 1 at -30 ⁰ C to 300 ⁰ C, preferably -15 ⁰ C to 150 ⁰ C and at Press from 1 to 20 bar, preferably from 1 to 10 bar in the presence of acidic catalysts and optionally in the presence of co-catalysts and / or solvents and / or dehydrating agents.

In formula (I), preference is given to 1-2 atoms X, in particular only one atom X, R ³ and R ^{4 being} simultaneously alkyl. Preferred alkyl is methyl; also usable are ethyl or C ₃ -C _e -alkyl radicals which may be straight-chain or branched. The X atoms in α-Stoliung to the di-phenyl-substituted C-atom (C-1) are preferably not dialkyl-substituted, on the other hand, the disubstitution with alkyl in the β-position in C-1 is preferred. It is particularly preferred that one x-atom is dialkyl-substituted in β-position and one X-atom is monoalkyl-substituted in β '-constition.

In some cases, the reaction is not quite consistent, d. h., Several different products may arise, so that the desired compound must first be isolated from a mixture. For details of the condensation, see Schnell, Chemistry and Pl.ysics of Polycarbonates, Interscience Publishers, New York 1964. Sometimes, the reaction can be controlled by selecting appropriate catalysts and reaction conditions such that the desired compound precipitates or crystallizes, facilitating its isolation.

The diphenols of the formula (I) according to the invention are particularly suitable for the preparation of high molecular weight, thermoplastic polycarbonates, which are characterized by high heat resistance in combination with a good other property profile.

The present invention thus also relates to the use of the diphenols of the formula (I) for the preparation of high molecular weight thermoplastic, aromatic polycarbonates.

It can be both a diphenol of the formula (I) to form homopolycarbonates and a plurality of diphenols of the formula

(I) to form copolycarbonates.

In addition, the diphenols of the formula (I) can also be used in admixture with other diphenols, for example those of the formula HO-Z-OH (VII), for the preparation of high molecular weight, thermoplastic, aromatic polycarbonates.

Suitable other diphenols of the formula HO-Z-OH (VII) are those in which Z is an aromatic radical having 6 to 30 C atoms, which may contain one or more aromatic nuclei, may be substituted and aliphatic radicals or other cycloaliphatic radicals as that of the formula (I) or heteroatoms may contain as bridge members.

Examples of diphenols of the formula (VII) are hydroquinone,

resorcinol,

dihydroxydiphenyls,

Bis (hydroxyphenyl) alkanes,

Bis- (hydroxyphenyl) -cycloalkanes,

Bis (hydroxyphenyl) sulfides,

Bis (hydroxyphenyl) ether,

ketones, bis- (hydroxyphenyl),

sulfones bis- (hydroxyphenyl),

Bis (hydroxyphenyl) sulfoxides,

a, a'-bis (hydroxyphenyl) -diisopropylbenzenes

and their nuclear alkylated and nuclear halogenated compounds.

These and other suitable other diphenols are e.g. in US Pat. Nos. 3,028,365, 2,998,335, 3,148,182, 3,275,601, 2,912, 3,313,367, 3,062,781, 29,701,31 and 2,999,846, German Laid-Open Patent Publication Nos. 1,570,703, 6,230,020, 206,352, 2,211,0956, French Patent No. 1,561,518 and the monograph "H. Schnell, Chemistry and Physics of Polycarbonates, Interscience Publishers, New York 1964 ".

Preferred other diphenols are, for example:

4,4'-dihydroxydiphenyl,

2,2-bis (4-hydroxyphenyl) -propane,

2,4-bis (4-hydroxyphenyl) -2-nethylbutan,

1,1-bis (4-hydroxyphenyl) -cyclohexane,

a, a'-bis (4-hydroxyphenyl) -p-diisopropylbbnzol,

2,2-bis (3-methyl-4-hydroxyphenyl) -propane,

2,2-bis- (3-chloro-4-hydroxyphenyl) -propane,

Bis (3,5-dimethyl-4-hydroxyphenyl) methane,

2,2-bis- (3,5-dimethyl-4-hydroxyphenyl) -propane,

8is- sulfone (3,5-dimethyl-4-hydroxyphenyl)

2,4-bis (3,5-dimethyl-4-hydroxyphenyl) -2-methylbutane,

1,1-bis (3,5-dimethyl-4-hydroxyphenyl) -cyclohexane,

α, α'-B i: (3,5-dimethyl-4-hydroxypher) yl) -p-diisopropylbenzene,

2,2-bis- (3,5-dichloro-4-hydroxyphenyl) -propanund

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

Particularly preferred diphenols of the formula (VII) are, for example:

2,2-bis (4-hydroxyphenyl) -propane,

2,2-bis- (3,5-dimethyl-4-hydroxyphenyl) -propane,

2,2-bis- (3,5-dichloro-4-hydroxyphenyl) -propane,

2,2-bis (3,5-dibromo-4-hydroxyphenyl) -propanund

1,1-bis (4-hydroxyphenyl) -cyclohexane.

In particular, 2,2-bis (4-hydroxyphenyl) propane is preferred.

The other diphenols can be used both individually and in a mixture.

The molar ratio of diphenols of the formula (I) to be used according to the invention to other diphenols which may be used, for example those of the formula (VII), is 100 mol% (I) to OMol% other diphenol to 2 mol% (I) to 98 mol % of other diphenol, preferably 100 mol% (I) to OMol% other diphenol to 5 mol% (I) to 95 mol% other diphenol and especially 100 mol% (l) to 0 mol% other diphenol to 10 mol% ( I) to 90 mol% of other diphenol and more particularly 100 mol% (I) to OMol% other diphenol to 20 mol% (I) to 80 mol% other diphenol.

The high molecular weight polycarbonates of the diphenols of the formula (I) according to the invention, if appropriate in combination with other diphenols, can be prepared by the known polycarbonate preparation processes. The various diphenols can be linked together both statistically and in blocks.

The present invention thus also provides a process for the production of high molecular weight thermoplastic, aromatic polycarbonates from diphenols, optionally chain terminators and optionally branching agents by the known methods of polycarbonate production, preferably by two-phase interfacial polycondensation, which is characterized in that as diphenols of the formula (I) in amounts of from IOOMol% to 2 mol%, preferably in amounts of from 100 mol% to 5 mol% and in particular in amounts of from IOOMol% to IOMol-%, and especially IOOMol-% to 20 Mol%, drawn in each case on the total molecular weight of diphenols used.

When Verzweigsr serve, if used, in a known manner, small amounts, preferably amounts between 0.05 and 2.0 mol% (based on diphenols used) of trifunctional or more than trifunctional compounds, in particular those having three or more than three phenolic hydroxyl groups. Some of the useful compounds having three or more than three phenolic hydroxyl groups are

phloroglucinol,

4,6-dimethyl-2,4,6-tri- (4-hydroxyphenyl) heptene-2,

4,6-dimethyl-2,4,6-tri- (4-hydroxyphenyl) heptane,

1,3,5-tri- (4-hydroxyphenyl) benzene,

1,1,1-tri- (4-hydroxyphenyl) ethane,

Tri- (4-hydroxyphenyl) phenylmethane,

2,2-BRS (4,4-bis (4-hydroxyphenyl) cyclohexyl) propane,

2,4-bis (4-hydroxyphenyl-isopropyl) -phenol,

2,6-bis- (2-hydroxy-5'-methylbenzyl) -4-methylphenol,

2- (4-hydroxyphenyl) -2- (2,4-dihydroxyphenyl) propane,

(4- (4-hydroxyphenyl-isopropyl) -phenyl) -ortho-hexa- terephthalate,

Tetra (4-hydroxyphenyl) methane,

Tetra (4- (4-hydroxyphenyl-isopropyl) -phenoxy) -methane and

1,4-bis - ((4 '-, 4' -dihydroxytriphenyl) methyl) benzene.

Some of the other trifunctional compounds are 2,4-dihydroxybenzoic acid, trimesic acid, cyanuric chloride and 3,3-bis (3-methyl-4-hydroxyphenyl) -2-oxo-2,3-dihydroindole.

As chain terminators for controlling the molecular weight are used in a known manner monofunctional compounds in conventional concentrations. Suitable compounds are for. As phenol, tert-butylphenols or other alkyl-C, -C ₇ -substituted phenols. For controlling the molecular weight, in particular small amounts of phenols of the formula (VIII) are suitable

(VIII)

wherein R represents a branched C ₈ and / or C ₉ alkyl radical. In the alkyl radical R, the proportion of protons in CH ₃ groups is preferably 47 to 89% and the proportion of protons in CH and CH ₂ groups is 53 to 11%; also preferably R is in the o- and / or p-position to the OH group, and more preferably the upper limit of the ortho-portion is 20%. The chain terminators are generally used in amounts of 0.5 to 10, preferably 1.5 to 8 mol%, based on diphenols.

The polycarbonates according to the invention can preferably be prepared in a manner known per se by interfacial polycondensation (cf., H. Schnell, "Chemistry and Physics of Polycarbonates", Polymer Reviews, Vol. IX, page 33 et seq., Interscience Publ., 1964) Diphenols of the formula (I) are dissolved in an aqueous alkaline phase To prepare co-polycarbonates with other diphenols, mixtures of diphenols of the formula (I) and the other diphenols, for example those of the formula (VII), are used Kettenabbrechor z. B. of the formula (VIII) may be added. Then, in the presence is an inert, preferably polycarbonate-dissolving, organic phase reacted with phosgene by the method of interfacial condensation the reaction temperature is between OX and 4O ⁰ C..

The optionally used 0.05 to 2 mol.% Of branching agents can be presented either with the diphenols in the aqueous alkaline phase or dissolved in the organic solvent added before the phosgenation.

In addition to the diphenols of the formula (I) and the other diphenols (VII), it is also possible to use their mono- and / or bischlorocarbonic esters, these being added dissolved in organic solvents. The amount of chain terminators and branching agents then depends on moles of diphenolate structural units of (I) and optionally of the other diphenols, such as (VII); Likewise, when using chlorocarbonic acid esters, the amount of phosgene can be correspondingly reduced in a known manner.

Suitable organic solvents for dissolving the chain terminators and optionally the branching agents and the chloroformates are, for example, methylene chloride, chlorobenzene, acetone, acetonitrile and mixtures of these solvents, in particular mixtures of methylene chloride and chlorobenzene. Optionally, the chain terminators and branching agents used can be dissolved in the same solvent.

For example, methylene chloride, chlorobenzene and mixtures of methylene chloride and chlorobenzene are used as the organic phase for Phasengronzflächenpolykondensation.

The aqueous alkaline phase used is, for example, aqueous NaOH solution.

The formation of polycarbonates according to the invention by interfacial polycondensation can be accelerated in a conventional manner by catalysts such as tertiary amines, in particular tertiary aliphatic amines such as tributylamine or triethylamine; the catalysts can be used in amounts of 0.05 to 10 mol%, based on moles of diphenols used. The catalysts can be added before the beginning of the phosgenation or during or after the phosgenation.

The polycarbonates of the invention can be separated in a known manner.

The high molecular weight, thermoplastic, aromatic polycarbonates according to the invention can also be prepared by the known homogeneous phase process, the so-called "pyridine process" and by the known melt transesterification process using, for example, diphenyl carbonate instead of phosgene. ,

The polycarbonates obtainable by the process according to the invention preferably have molecular weights M w (weight average, determined by gel chromatography after prior calibration) of at least 10,000 g / mol, more preferably from 10,000 to 300,000 g / mol. Insofar as the polycarbonates according to the invention are used as injection molding material, particularly preferred molecular weights are between 20,000 and 80,000 g / mol. As far as the invention

Polycarbonates are used as cast films, in particular molecular weights Mw between 100,000 and 250,000 g / mol are preferred. For the production of extrusion films, polycarbonates according to the invention with Mw between 25,000 and 150,000 g / mol are preferred. The polycarbonates of the invention may be linear or branched, they are homopolycarbonates or copolycarbonato based on the diphenols of the formula (I).

The present invention thus also relates to high molecular weight thermoparable aromatic polycarbonates having Mw (weight average molecular weights) of at least 10,000, preferably from 10,000 to 300,000 and, for applications in the injection molding sector, in particular from 20,000 to 80,000, obtainable by the process according to the invention from diphenols of the formula (I) which are linear or branched.

The present invention accordingly also relates to high molecular weight, thermoplastic, aromatic polycarbonates having Mw (weight average molecular weights) of at least 10,000, preferably from 10,000 to 300 ° C / mol and, for applications in the injection molding sector, in particular from 20,000 to 80,000, the bifunctional carbonate structural units of the formula ( la)

(La).

X, R ¹ , R ² , R ³ , R ⁴ and m have the meaning given for the formula (I), in amounts of from 100 mol% to 2 mol%, preferably in amounts of from 100 mol% to 5 mol% and in particular in amounts of from 100% to 10% by mol and more particularly from 100% to 20% by mol, based in each case on the total amount of 100% by mol of difunctional carbonate structural units in the polycarbonate.

The polycarbonates according to the invention thus contain in each case 100 mol% of complementary amounts of other difunctional carbonate structural units, for example those of the formula (VII a)

(Vila)

Thus OMol-% (inclusive) to 98MoI- ⁰ / inclusive, preferably OMol-% to 95Mol-% and in particular OMol-% to 90 mol% and very particularly preferably OMol-% to 80Mol-%, based in each case on the total amount ( of 100 mol%) of difunctional carbonate structural units in the polycarbonate.

Polycarbonates based on cycloaliphatic bisphenols are known in principle and z. For example, in EP-A 164476, DE-OS 3345945, DE-OS 2063052, FR-PS 1427998, WO8000348, BE-PS 785189 described. They often have relatively high glass transition temperatures, but other important physical properties such as UV and heat aging stability are inadequate.

It has now surprisingly been found that, as already mentioned, by incorporating the diphenols of the formula (I) according to the invention new polycarbonates are obtained with high heat resistance, which otherwise have a good property picture. This applies in particular to the polycarbonates based on the diphenols (I), in which "m" is 4 or 5, and especially for the polycarbonates based on diphenols (I b)

(Ib)

R ¹ and R ² independently of one another have the meaning given for formula (I) and are particularly preferably hydrogen. Thus, the subject of the invention are preferably polycarbonates in which in the structural units of the formula (Ia) m = 4 or 5 and especially those having structural units of the formula (Ic)

(Lc),

R 'and R ^{2 have} the meaning given for formula (I s) , but are particularly preferably hydrogen.

These polycarbonates based on the diphenols of the formula (I b), in which, in particular, R ¹ and R ^{2 are} hydrogen, furthermore have good UV stability and good flow behavior in the melt for high heat resistance, which is not to be expected

The free combinability with other diphenols, in particular with those of the formula (VII), moreover, the polycarbonate properties can be varied in a favorable manner.

The isolation of the polycarbonates obtainable by the process according to the invention is carried out in a known manner by separating the organic phase obtained in interfacial process, washed neutral and electrolyte-free and then isolated as granules, for example via a evaporation extruder.

The polycarbonates according to the invention may be added before or after their processing, the usual additives for thermoplastic polycarbonates such as stabilizers, mold release agents, pigments, flame retardants, antistatic agents, fillers and reinforcing agents in the usual amounts.

Specifically, for example, carbon black, graphite, diatomaceous earth, kaolin, clays, CaF ₂ , CaCO ₃ , aluminum oxides, glass fibers, Bai iumsulsat and inorganic pigments can be added both as fillers and as Nigungsierungsmittcl, and as mold release agents such as glycerol stearate, pentaerythritol tetrastearate and Trimethylolpropantristearat.

The polycarbonates of the invention can be processed to Formkr.rperri by extruding, for example, the isolated in a known manner polycarbonates into granules and processed this granules optionally after addition of the above additives by injection molding to various articles in a known manner.

The polycarbonates according to the invention can be used as molded articles wherever the hitherto known polycarbonates have been used, ie in the electrical sector and in the construction sector for coverings and glazings, namely when increased heat resistance combined with good processability, ie when complicated components of high heat resistance are required.

Further uses of the polycarbonates according to the invention:

As optical data storage, for example compact discs:

The production of such data storage is known (see, for example, J. Hennig, Lecture at the conference "New Polymers" Bad Nauheim 14 / 15.04.1986 "polymers as substrates for optical disk storage" or Philips Techn. Rev.33,178-180,1973, no. 7 and 33,186-189,1973 NoI 7).

For the production of safety discs.

Safety discs usually have a thickness of 2 mm to 10 mm and can be vapor-deposited with SiO _x , in which χ has a value of 1 to 2, or be used in conjunction with glass panes. Safety discs are known to be required in many areas of buildings, vehicles and aircraft, as well as shields and helmets of Mutzen.

As paint raw materials.

For the production of blown bodies (see, for example, US Pat. No. 2,964,794).

For the manufacture of translucent panels, in particular of cellular panels, for example for covering buildings such as railway stations, greenhouses and lighting installations.

For the production of foams. (See for example DE-AS 1031 507).

For the production of threads and wires (See for example DE-AS 1137167 and DE-OS 1785137).

As a translucent plastic with a content of glass fibers for lighting purposes. (See, for example, DE-OS 1544020).

For producing precision injection molded particles, such as lens mounts. To this end, ma> ^D olycarbonates having a content of glass fibers, optionally containing in addition about 1 wt .-% to 10Gow .-% MoS ₂ , based on total weight.

For the production of optical device parts, in particular lenses for photo and film cameras. (See, for example, DE-OS 2701173).

As a light transmission carrier, in particular as a light guide cable. (See, for example, EP-OS 0089801).

As Elektroisolierstoffe for electrical conductors.

As carrier material for organic photoconductors.

For the production of luminaires, e.g. Scheinv.erferlampen, as so-called "head-lamps" or Streulichtscheiben.

In particular, films can be made from the high molecular weight aromatic polycarbonates of the invention. The

Films have preferred thicknesses between 1 and 1500pm, especially preferred thicknesses between 10μm '900pm.

The resulting films can be stretched in a conventional manner monoaxially or biaxially, preferably in the ratio 1: 1.5

The films can be made according to the known methods for film production h, z. B. by extrusion of a polymer melt through a slot die, by blowing on a Folienbiasmaschine, deep drawing or casting. In this case, a concentrated solution of the polymer is poured in a suitable solvent on a flat surface, the solvent evaporates and lifts the film formed from the pad.

The films can be drawn in known manner at temperatures.-Room temperature and a temperature at which the viscosity of the polymer melt is not yet too low, allgemeinenτι generally up to about 370 ° C, drawn on known devices.

Dio film production by casting the polycarbonate solutions takes place, for example, by pouring concentrated solutions of the polycarbonate in a suitable solvent on flat surfaces and then evaporates at a temperature control of the flat surfaces between room temperature and 150 ° C solvent. It is also possible to apply the concentrated solutions of the polycarbonates to liquids which have a higher density than that of the concentrated solutions, not with the. solvents used are compatible and do not dissolve the polycarbonate, and after spreading the films win by Verdarr pfen the solvent used for the polycarbonate and optionally also the liquid of higher density.

The films of the invention have a particularly high heat resistance and are permeable to many gases: nevertheless good selectivity. They can therefore be used advantageously as a membrane for gas permeation who Jen.

It is possible to use these slides on their own.

It is of course also possible to use them to produce composite films with other plastic films, in which case, depending on the desired application and end properties of the composite film, all known films can be considered as partners. For example, a composite of two or more films can be made by stacking the individual films, including the polycarbonate film, and pressing them under suitable temperatures determined by the softening points of the individual films. The known film coextrusion process can be used.

The composite films are produced by first producing the films of the individual components in a known manner or in the manner described above in an optimum temperature control. Subsequently, the uncooled films are brought without greater stretching to a common temperature, which is preferably between room temperature and 37O ⁰ C. The films are then brought together via rollers and briefly pressed.

In this case, a pressure between 2 and SOObar can be used. The process can also be carried out with more than one other film than that of the polycarbonates, wherein, for example, first the other films are brought together in the previously known manner and then pressed with the film of the polycarbonates under the pressure described above.

The films or composite films can be prepared in a known manner beyond as a homogeneous membrane, composition membrane or asymmetric membrane or used. The membranes, films or composite films can flat a hollow body of different geometries form - cylindrical, spherical, tubular - or even Hohlfascrn be. Such moldings may have been prepared by the methods known to those skilled in the art.

Depending on the application, various polymers which are listed below can be used as polymers from which films can be produced for the production of composite films with the polycarbonate films of the invention. Depending on the application, it is thus also possible to achieve gas-impermeable composite films which are more advanced than the prior art. ^! ne have better heat resistance, or you can get heat-resistant, gas-permeable composite films, depending on the choice of the partners.

In the following, materials are provided which provide films which can be combined with the films according to the invention. These materials are referred to as components (b).

As component (b) are suitable thermoplastics

b 1) dmorphe thermoplastics, preferably those having a glass transition temperature of more than 40 ⁰ C, in particular from 60 ° C to

220 ° C, and b2) semi-crystalline thermoplastics, preferably those having a melting temperature of more than 6O ⁰ C, in particular from 80 ⁰ C to <00 ° C.

Elastomers for the component b) are b3) are those having a glass transition temperature of below ⁰ C, preferably less than -1O ⁰ C and especially from -15 ⁰ C to · - have 14O ⁰ C,.

Examples of amorphous thermoplastics b 1) are amorphous polymers from the class of polycarbonates, polyamides, polyolefins, polysulfones, polyketones, thermoplastic vinyl p ^ ¹ "nerisato as Polymethylacrylsäureester or Homi 'polymers of aromatic vinyl compounds, copolymers of Vinylaromati η or graft polymers of vinyl monomers on rubbers, Polyethers, polyimides, thermoplastic polyurethanes, aromatic polyester carbonates) and liquid-crystalline polymers Examples of crystalline thermoplastics b2 * are aliphatic polyesters, polyacrylic sulfides and the partially crystalline representatives of the thermoplastics subsumed under b1) above.

Examples of elastomers b3) are the most varied rubbers such as ethylene-propylene rubber polyisoprene, polychloroprene, polysiloxanes, atactic polypropylene, diene, olefin and acrylate rubbers and natural rubbers, styrene-butadiene block copolymers, ethylene copolymers with vinyl acetate or with (meth) acrylic esters, elastic polyurethanes where not subsumed as thermoplastics under b 1) or b 2) and elastic polycarbonate-polyether block copolymers.

Amorphous thermoplastics b 1) are in particular polycarbonates (except the polycarbonates according to the invention). Polycarbonates may be both homopolycarbonates and copolycarbonates, they may be both linear and branched. Particularly preferred bisphenol for the polycarbonates is bisphenol-A.

The molecular weights M w (weight average molecular weight, determined by gel permeation chromatography in tetrahydrofuran) of the thermoplastic polyarbonates are between 10,000 and 300,000, preferably between 12,000 and

The thermoplastic polycarbonates are also usable individually as .vohl 'n mixtures as component b).

Preferred other thermoplastics are also aliphatic, thermoplastic polyesters, particularly preferably polyalkylene terephthalates, for example those based on ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol and 1,4-bis-hydroxymethyl-cyclohexane.

The molecular weights (Mw) of these polyalkylene terephthalates are between 10,000 and 80,000. The polyalkylene terephthalates can be obtained by known processes, for example from dialkyl terephthalate and the corresponding diol by transesterification (see, for example, US patents 2647885, 2643989, 23534028, 25578660, 2742494, 2901466).

Other preferred thermoplastics are thermoplastic polyamides.

All partially crystalline polyamides, in particular polyamide-6, polyamide-6,6 and partially crystalline copolyamides based on these two components, are suitable. Also suitable are partially crystalline polyamides whose acid component consists in particular entirely or partially of adipic acid or caprolactone, of terephthalic acid and / or isophthalic acid and / or suberic acid and / or sebacic acid and / or azelaic acid and / or dodecanedicarboxylic acid and / or adipic acid and / or a cyclohexanedicarboxylic acid, and their diamine components wholly or partly consist in particular of m- and / or p-xylylenediamine and / or hexamethylenediamine and / or 2,2,4- and / or 2,4,4-trimethylhexamethylenediamine and / or isophoronediamine and / or 1,4-diaminobutane and their compositions are known in principle from the prior art (see, for example, Encyclopedia of Polymers, Vol. 11, p.315ff.).

Also suitable are partially crystalline polyamides which are prepared wholly or partly from lactams having 6 to 12 C atoms, if appropriate with the concomitant use of one or more of the abovementioned starting components.

Particularly preferred semi-crystalline polyamides are polyamide-6 and polyamide-6,6 or copolyamides with a low content, up to about 10% by weight of other components.

Suitable polyamides are also amorphous polyamides obtained, for example, by polycondensation of diamines, such as, for example, hexamethylenediamines, decamethylenediamine, 2,2,4- and 2,4,4-trimethylhexamethylenediamine, m- or p-xylylenediamine, bis- (4-aminocyclohexyl) methane, mixtures of 4,4'- and 2,2'-diaminodicyclohexylmethanes, 2,2-bis- (4-aminocyclohexyl) -propane, S.S'-dimethylM '' - diamino-dicyclohexylmethane, S-aminoethyl-S. ö ^ -trimethyl-cyclohexylamine, 2,5-bis (aminomethyl) norbornane, 2,6-bis (aminomethyl) norbornane, 1,4-diamino-methylcyclohexane u'id of any mixtures of these diamines, with dicarboxylic acids such as for example, with oxalic acid, adipic acid, azelaic acid, decanedicarboxylic acid, heptadecanedicarboxylic acid, 2,2,4-trimethyladipic acid, 2,4,4-trimethyladipic acid, isophthalic acid and terephthalic acid and with any desired mixtures of these dicarboxylic acids. Thus, amorphous copolyamides are also included, which are obtained by polycondensation of several of the aforementioned diamines and / or dicarboxylic acids.

Furthermore, amorphous copolyamides are included, which are prepared with the concomitant use of ω-aminocarboxylic acids such as ω-aminocaproic acid, ω-aminoundecanoic acid or ω-aminolauric acid or of their lactams.

Particularly suitable, amorphous, thermoplastic polyamides are those selected from isophthalic acid, hexamethylenediamine and other diamines such as 4,4'-diaminodicyclohexylmethane, isophoronediamine, 2,2,4- and 2,4,4-trimethylhexamethylenediamine, 2,5- and / or 2,6-bis (aminomethyl) norbornane, those obtainable from isophthalic acid, M'-diamino-di-cyclohexylmethane and ω-caprolactam, those derived from isophthalic acid, 3,3-dimethyl-4, 4'-diamino-dicyclohexylmethane and ω-laurolactam, and those obtainable from terephthalic acid and the isomeric mixture of 2,2,4- and 2,4,4-trimethylhexamethylenediamine.

Instead of pure 4,4'-diaminodicyclohexylmethane, it is also possible to use mixtures of diisocyanodicyclohexylmethanes which are composed of 70 to 99% by mol of the 4,4'-diamino isomer

1 to 30 mol% of the 2,4'-diaminoisomer

0 to 2 mol% of the 2,2'-diaminoisomer

and, optionally, correspondingly higher-condensed diamines obtained by hydrogenation of technical grade diaminodiphenylmethane.

Suitable thermoplastic polyamide 3 may also consist of mixtures of semicrystalline and amorphous polyamides, wherein preferably the proportion of amorphous polyamide is less than the proportion of partially crystalline polyamide. The amorphous polyamides and their preparation are known from the prior art (see, for example, Ulimann, Enzyklopadie d. Technical chemistry, Volume 19, p.

Preferred other thermoplastics b) are also thermoplastic linear or branched polyarylone sulfides. They have structural units of the general formula

WR ₄ R ₃

where Ri to R _{4 may be} identical or different and Ci-Ce-alkyl, phenyl or Wassorstol. mean. The polyarylene sulfides may also contain diphanyl cinities. Polyarylene sulfides and their preparation are known (see for example US-PS 3354129 and EP-A 0171021).

Further preferred other thermoplastics b) are thermoplastic polyarylene sulfones.

Suitable polyarylene sulfones have weight average molecular weight Mw (measured by the light scattering method in CHCl ₃ ) of from 1000 to 200,000, preferably from 20,000 to 60,000.

Examples are the Polyai _r available by known methods c.-oj |! Fone of 4,4'-Dichloridphenvlsulfon and one.

Bisphenol, in particular 2,2-bis (4-hydroxyphenyl) propane, with Mw of 2C00 to 200,000.

Polyarylene sulfones are known (see for example US-PS 3264536, DE-AS 1794171, GB-PS 1264900, US-PS 3641207, EP-A-OO 38028, DE-OS 3601419 and DE-OS 3601420). The polyarylene sulfones can also be branched in a known manner (see, for example, DE-OS 2305413).

Preferred other thermoplastics b) are also known thermoplastic polyphenylene oxides, preferably poly (2,6-dialkyl-1,4-phenylene oxides) having molecular weights Mw (weight average, measured by light scattering in chloroform) of from 2000 to 100,000, preferably from 20,000 to 60,000.

They can, as is known, be obtained by oxidative condensation of 2,6-dialkylphenols with oxygen in the presence of copper salts and tertiary amines as catalyst (see for example DE-OS 2126434 and US-PS330Ü975).

Suitably si.:J in particular poly [2,6-di (C 1 -C 4 alkyl) -1,4-phtnoxides, e.g. Poly (2,6-dimethyl-1,4-phenylene oxide).

Preferred other thermoplastics b) are also aromatic polyether ketones themselves (see, for example, GB-PS 1078234, US-PS 4010147 and EP-OS 0135938), except those based on diphenols of the formula I.

They contain the recurring structural element

-OEOE ¹ -,

where -E'- is the divalent radical of a bisaryl ketone and -O-E-O- is a divalent diphenolate radical.

For example, according to GB-PS 1078234, they can be prepared from dialkalidiphenolates of the formula alkali-O-E-O-alkali and bis (haloaryl) -ketones of the formula Hal-E'-Hal (with Hal = halogen). A suitable Dialkalidiphenolat is z. B.

that of 2,2-bis (4-hydroxyphenyl) propane, a suitable bis-i-haloaryl ketone is 4,4'-dichlorobenzophenone.

Preferred other thermoplastics b) s ^: nd also thermoplastic vinyl polymers.

Vinyl polymers for the purposes of this invention are homopolymers of vinyl compounds, copolymers of vinyl compounds and graft polymers of vinyl compounds on rubbers.

Homopolymers and copolymers suitable according to the invention are those of styrene, α-methylstyrene, acrylonitrile, methacrylonitrile, C 1 -C ₁₂ -cycloalkyl esters of (meth) acrylic acid, C 1 -C ₄ -carboxylic acid vinyl esters, where dio copolymers are obtainable from mixtures of these vinyl compounds by known methods.

The homopolymers or copolymers should have intrinsic viscosities (Staudinger indices) of between 0.3 and bdl / g (measured at 2 ° C. in toluene in a known manner).

Geei, iete vinyl polymers are, for example, thermoplastic poly-C, -C ₄ -alkalymothacrylate, for example, those of methyl, ethyl, propyl or Butylmethacrylsäureescers, preferably the methyl or ethyl methacrylsäureesters. Both homopolymers and copolymers of these methacrylic esters are to be understood as meaning 20. In addition, other, ethylenically unsaturated copolymerizable monomers such as) (meth) acrylonitrile, (a-methyl> styrene, bromostyrene, vinyl acetate, acrylic acid C ^ Ce alkyl ester, (meth) acrylic acid, ethylene, propylene and N-vinylpyrrolidone in be polymerized in minor amounts.

The thermoplastic poly-C 1 -C ₄ -alkyl methacrylates which are suitable according to the invention are known from the literature or obtainable by processes known from the literature.

Suitable vinyl polymers are also copolymers of styrene or α-methylstyrene and acrylonitrile, which optionally contain up to 40% by weight of esters of acrylic acid or methacrylic acid, in particular methyl methacrylate or n-butyl acrylate.

Styrene derivatives must be included as monomers in any case. The styrene derivatives are in proportions zwische :. 100 and 10% by weight, preferably between 90 and 20% by weight, particularly preferably between 80 and 30% by weight, which are prepared by conventional processes such as radical polymerization in bulk, solution, suspension or emulsion, but preferably by free-radical emulsion polymerization to be obtained in water.

Suitable graft polymers are formed by polymerization of the abovementioned vinyl monomer or vinyl monomer polymers in the presence of rubbers having glass transition temperatures <0.degree. C., preferably <-20.degree. The graft polymers generally contain from 1 to 85% by weight, preferably from 10 to 80% by weight, of rubber. The graft polymers can be prepared by conventional methods in solution, mass or emulsion, preferably in emulsion, wc! vinyl monomer mixtures may be simultaneously or successively graft polymerized.

Suitable rubbers are preferably diene rubbers and acrylate rubbers.

Diene rubbers are, for example, polybutadiene, polyisoprene and copolymers of butadiene with up to 35% by weight of comonomers such as styrene, acrylonitrile, methyl methacrylate and C 1 -C -alkyl acrylates.

Acrylate rubbers are, for example, crosslinked, partially polymeric emulsion polymers of C 1 -C -alkyl acrylates.

in particular C ₂ -C ₆ -alkyl acrylates, optionally mixed with up to 15% by weight of other unsaturated monomers such as styrene, methyl methacrylate, butadiene, vinylmethyl ether, acrylonitrile, and ai_3 at least one polyfunctional crosslinker such as divinylbenzene, glycol bis-acrylates, Bisacrylamides, triallyl phosphoric acid esters, triallyl citric acid esters, allyl esters of acrylic acid and methacrylic acid, triallyl isocyanurate, it being possible for the acrylate rubbers to contain up to 4% by weight of the crosslinking comonomers.

For the preparation of the graft polymers, mixtures of diene with acrylate rubbers and rubbers mif a core-shell structure are suitable.

The rubbers must be in the form of discrete parts for graft polymerization, e.g. B. as latex. These particles have i. a.

average diameter from 10nm to 2000nm.

The graft polymers may be produced by known methods, for example by radical emulsion graft polymerization of vinyl monomers in the presence of rubber latices at temperatures of from 50 to 9O ⁰ C, using water-soluble initiators, such as peroxodisulfate, or by means of redox initiators.

Free-radically prepared emulsion graft polymers are preferred on particulate, highly crosslinked rubbers (diene or alkyl acrylate rubbers) with gel contents> 80% by weight and average particle diameters (d50) of ί t to 800 nm. Particularly suitable are industrially customary ABS polymers.

Mixtures of vinyl homopolymers and / or vinyl copolymers with graft polymers are also suitable.

Preferred other thermoplastics b) are also thermoplastic polyurethanes. These are reaction products of diisocyanates, all or predominantly aliphatic oligo- and / or polyesters and / or ethers and one or more chain extenders. These thermoplastic polyurethanes are substantially linear and have thermoplastic processing characteristics.

The thermoplastic polyurethanes sVid are known or can be prepared by known methods (see, for example, US Pat. No. 3,214,411, JHSaunders and KC Frisch, "Polyurethanes, Chemistry and Tccniiuiogy", VoIII, pages 299-451, Interscience Publishers, New York, 1964 and Mobay Chemical Coporation , "A Processing Handbook for Texin Urethane Elastoplastic Materials", Pittsburgh, PA).

Examples of starting materials for preparing the oligoesters and polyesters are adipic acid, succinic acid, suberic acid, sebacic acid, oxalic acid, methyladipic acid, glutaric acid, pimelic acid, azelaic acid, phthalic acid, terephthalic acid and isophthalic acid

 Adipic acid is preferred here.

Examples of suitable glycols for preparing the oligoesters and polyesters are ethylene glycol, 1,2- and 1,3-propylene glycol, 1,2-, 1,3-, 1,4-, 2,3-, 2,4-butanediol, hexanediol , Bishydroxymethylcyclohexan, diethylene glycol and 2,2-dimethyl-propylene glycol into consideration. In addition, together with the glycols, small amounts, up to 1 mole%, of tri- or higher functional alcohols, e.g. As trimethylolpropane, glycerol, hexanetriol, etc. are used.

The resulting hydroxyl-oligo- or polyester have a molecular weight of at least 600, a hydroxyl number of about 25 to 190, preferably about 40 to 150, an acid * / ¹ ! -.! from about 0.5 to 2 and a water content of about 0.01 to 0.2%. Oligoesters or polyesters are also oligomeric or polyrear lactones, such as, for example, oligo-caprolactone or polyalkrolactone, and aliphatic polycarbonates, for example polybutanediol (1,4) carbonate or polyhexanediol (1,6) carbonate.

A particularly suitable oligoorest that can be used as a starting material for the thermoplastic polyurethanes is made from adipic acid and a glycol having at least one primary hydroxyl group. The condensation is terminated when an acid number of 10, preferably about 0.5 to 2 is reached.

The resulting during the reaction water is separated at the same time or afterwards, so that the water content at the end in the range of about 0.01 to 0.05%, preferably 0.01 to 0.02.

Oligo- or polyethers for the preparation of the thermoplastic polyurethanes are, for example, those based on tetramethylene glycol, propylene glycol and ethylene glycol

 Polyacetals are also to be understood and used as polyethers.

The oligoethers or polyethers should have average molecular weights Mn (number average, determined by the OH number of the products) of from 600 to 2000, preferably from 1000 to 2000.

As the organic diisocyanate, 4,4'-diphenylmethane diisocyanate is preferably used to prepare the polyurethanes. It should contain less than 5% 2,4'-diphenylmethane diisocyanate and less than 2% of the dimer of diphenylmethane diisocyanate. It is further desirable that the acidity, calculated as HCl, be in the range of about 0.005 to 0.2%. The acidity, calculated as% HCl, is determined by extraction of the chloride from the isocyanate in hot, aqueous methanol solution or by liberation of the chloride upon hydrolysis with water and titration of the Extr iktes with standard silver nitrate solution to the chloride present therein To obtain ion concentration.

Other diisocyanates may also be used to prepare the thermoplastic polyurethanes, for example, the diisocyanates of ethylene, ethylidene, propylene, butylene, cyclopentylene-1,3, cyclohoxylene-1,4, cyclohexylone-1,2, 2,4-tolylene, of 2,6-tolylene, p-phenylene, n-phenylene, xylene, 1,4-naphthylene, 1,5-naphthylene, 4,4'-D: phenylene, 2,2-diphenylpropane 4,4'-diisocyanate, the azobenzene-4,4'-diisocyanate, the diphenylsulfone-4,4'-di-cyanate, the dichlorohexanemethylene diisocyanite, the pentamethylene diisocyanate, the hexamethylene diisocyanate, the 1-chlorobenzene, adiisocyanate, the furfuryl diisocyanate, the di-cyclohexylmethane diisocyanate, the isophorone diisocyanate, the diphenylethane diisocyanate and the bis (isocyanatophenyl) ether of ethylene glycol, butanediol, etc.

As chain extenders it is possible to use organic difunctional compounds containing active hydrogen reactive with isocyanates, e.g. Diols, hydroxycarboxylic acids, dicarboxylic acids, diamines and alkanolamines) and water. As such are, for example, ethylene, propylene, butylene glycol, 1,4-butanediol, butanediol, butynediol, xylylene glycol, amylene glycol, 1,4-phenylene-bis-.beta.-hydroxyethylethor, 1,3-phenylene-bis-ß- hydroxyethyl ether, bis-ihydroxymethylcyclohoxane), hexanediol, adipic acid, ω-hydroxycaproic acid, thiodiulycol, ethylenediamine, propylene, butylene, hexamethylene cyclohexylene, phenylene, tolylene, xylylenediamine, diaminodicyclohexylmethane, isophoronediamine, 3,3'-dichlorobonzidine, 3,3'-dinitrobenzidine, ethanolamine, aminopropyl alcohol, 2,2-dimethyl-propanolamine, 3-aminocyclohexyl alcohol and p-aminobenzyl alcohol. The molar ratio of oligo- or polyester to bifunctional chain extender ranges from 1: 1 to 1:50, preferably 1: 2 to 1:30.

In addition to difunctional chain extenders, it is also possible to use minor amounts of up to about 5 mol%, based on moles of bifunctional chain extenders, trifunctional or more than trifunctional chain extenders.

Such trifunctional or more than trilunktionclle chain extenders are, for example Glycr ^r in, trimethylolnoprane, hexanetriol, pentaerythritol and triethanolamine.

Monofunctional components, for example butanol, can also be used to prepare the thermoplastic polyurethanes.

The diisocyanates, oligoesters, polyesters, polyethers, chain extenders and monofunctional components mentioned as building blocks for the thermoplastic polyurethanes are either known from the literature or obtainable by methods known from the literature.

The known preparation of the polyurethanes can be carried out, for example, as follows:

Thus, for example, the oligo- or polyesters, the organic diisocyanates and the chain extenders can be heated to a temperature of about 50 to 220 ° C per se and then mixed. Preferably, the oligo- or polyesters are first heated individually, then mixed with the chain extenders and the resulting mixture is mixed with the preheated isocyanate.

The mixing of the starting components for the preparation of the polyurethanes can be carried out with any mechanical stirrer which allows intensive mixing within a short time. If the viscosity of the mixture should prematurely increase too rapidly during stirring, either the temperature may be lowered or a small amount (0.001-0.05% by weight based on ester) of citric acid or the like may be added to reduce the rate of the reaction , To increase the reaction rate suitable catalysts, such as. B. tertiary amines, which are mentioned in US Patent 2729618, are used.

Preferred other thermoplastics are also so-called "LC polymers." LC polymers are polymers which can form liquid-crystalline melts, and such polymers, which are also referred to as "thermotropic", are well known (see, for example, EP-OS 0131846, EP -OS 0132637 and EP-OS 0134959). In the mentioned literary galleries further literature is attracted and moreover the determination of the liquid-crystalline state of polymer melts is described.

"LC polymers" are, for example, aromatic polyesters based on optionally substituted p-hydroxybenzoic acid, optionally substituted iso- and / or terephthalic acids, 2,7-dihydroxynaphthalene and other diphenols (EP-OS 0131846), aromatic polyesters based on optionally substituted p Hydroxybenzoic acid, diphenols, carbonic acid and optionally aromatic dicarboxylic acids (EP-OS 0132637) and aromatic polyester based on optionally substituted p-hydroxybenzoic acid, 3-chloro-4-hydroxybenzoic acid, isophthalic acid, hydroquinone and 3,4'- and / or 4, 4'-dihydroxydiphenyl, 3,4'- and / or 4,4'-dihydroxydiphenyl ether and / or 3,4'- and / or 4,4'-dihydroxydiphenyl sulfide (EP-OS 0134959).

The LC polymers have a persistence length at room temperature between 18 and 1300 A, preferably between 25 and 300 Å, in particular between 25 and 150 A.

The persistence length of a polymer at room temperature characterizes the mean entanglement of a molecular chain in a dilute solution under theta conditions (see, for example, BPJ Flory, Principles of Polymer Chemistry, Cornell Univ. Press, Ithaca, New York) and half of the Kuhn's The persistence length can be determined with different methods in dilute solutions, eg by light scattering and small angle X-ray measurements After suitable preparation, the persistence length can also be determined with the help of the neutron small angle scattering in the solid state Further theoretical and experimental methods are eg in JH Wendoff in "Liquid Crystalline Order in Polymers", eg A. Blumstein, Academic Press 1978, p. 16ff. as well as in the "S.M. Aharoni, Macromolecules 19, (1986), p.429ff. ".

Preferred other thermoplastics are also aromatic polyester carbonates.

Aromatic polyesters and polyestercarbonates which can be used according to the invention as thermoplastic b) are prepared from at least one aromatic bisphenol, e.g. of the formula (VII), from mindectens an aromatic dicarboxylic acid and optionally carbonic acid. Suitable aromatic dicarboxylic acids are, for example, orthophthalic acid, terephthalic acid, isophthalic acid, tert-butylisophthalic acid, 3,3'-diphenyldicarboxylic acid, 4,4'-diphenyldicarboxylic acid, 4,4'-8-benzophenone dicarboxylic acid, 3,4'-benzophenone dicarboxylic acid, 4,4'-diphenyl ether dicarboxylic acid , 4,4'-diphenylsulfonedicarboxylic acid, 2,2-bis (4-carboxyphenyl) -propane, trimethyl-3-phenylindane-4,0'-dicurbonic acid.

Of the aromatic dicarboxylic acids, terephthalic acid and / or isophthalic acid are particularly preferably used.

Aromatic polyesters and polyester carbonates can be prepared by processes known in the literature for polyester or polycarbonate production, for example, see e.g. B. by homogeneous solution method, by melt transesterification method and by the two-phase interface method. Preferably, melt transesterification processes, and especially the two-phase interfacial process, are used.

For example, melt transesterification methods (acetate method and phenyl ester method) are disclosed in U.S. Patent Nos. 3,494,885, 4,386,186, 4,661,580, 4,680,371 and 4,680,372, EP-A-26120, 26121, 26684, 28030, 398, 9, 100, 97970, 790, 75, 16, 699, 194919 and 240301 and DE-A 1495626,2232977. The two-phase interface process is described, for example, in EP-A 68014.88322, 134898, 5175, 750, 82189, 219 708, 272426, DE-OS 2940024, 3007934, 3440020 and in Polymer Reviews, Volume 10, "Condensation Polymers by Interfacial and Solution Methods Paul W. Morgan, Interscience Publishers, New York 1965, Chap. VIII, p.325, Polyester.

In the acetate process, bisphenol diacetate or, in the phenyl ester process, bisphenol, aromatic dicarboxylic acid or diphenyl ester of the aromatic dicarboxylic acid and optionally diphenyl carbonate are generally reacted with phenol elimination and optionally CO ₂ elimination to give the polyester or polycarbonate. In the two-phase interfacial process, starting materials are used for the preparation of polyesters and polyestercarbonates, generally alkali bisphenolate, aromatic dicarboxylic acid dichloride and optionally phosgene.

In this condensation reaction, the polyester or polyester carbonate are prepared by alkali chloride formation. In general, the salt formed is dissolved in the aqueous phase, while the polyester formed or the polyester carbonate formed is dissolved in the organic phase and isolated therefrom.

Preferred elastomers b3) for component b) for the preparation of the mixtures according to the invention are the above-mentioned polyurethanes, as far as they are elastic, styrene, butadiene block copolymers, which may be partially hydrogenated (for example Kraton G ^s of Shell), which are described above for the Graft polymers mentioned rubbers, the graft polymers themselves, as far as they are elastic and elastic polycarbonate-polyether block copolymers.

These elastomers are known.

The films, or Verbundfoi on can be flat, hollow, spherical, tubular and hollow fiber-shaped.

Such films are available by known methods by deformation, deep drawing, blowing, etc.

The films according to the invention, in particular the composite films, are used, for example, for cooking and oven-tight sealed packaging and for microwave-resistant packaging, depending on with which component b) the composite film according to the invention is constructed.

The composite films according to the invention can be produced by coextrusion of the thermoplastics with the polycarbonates according to the invention in one operation.

The films of the polycarbonates according to the invention and the inventive composite films based on these films of the polycarbonates according to the invention can be used as homogeneous membranes, composition membranes or asymmetric membranes.

embodiments

Example A.1

Preparation of the diphenol of the formula (II)

In a 1-liter round bottom flask equipped with stirrer, dropping funnel, thermometer, reflux condenser and gas inlet tube are charged 7.5 mol (705 g) of phenol and 0.15 mol (30.3 g) of dodecylthiol and at 28 to 30 ^c C with dry HCl gas saturated. To this solution, a solution of 1.5 mol (210 g) Dihydroisophoron OSö-trimethyl-cyclohexane-i-on) and 1.5 mol (151 g) of phenol are added dropwise within 3 hours, further passed HCl gas in the reaction solution becomes. After the end of the dropping, HCl gas is introduced for a further 5 hours. It is allowed to nachroagieren for 8 hours at room temperature. Subsequently, the excess phenol is removed by steam distillation. The remaining residue is extracted twice with petroleum ether (60-90) and once with hot methylene chloride and filtered off.

Yield: 370g

Melting point: 205 to 207 ° C

Example A.2

Preparation of the diphenol of the formula (II)

In a stirred apparatus with stirrer, thermometer, reflux condenser and gas inlet tube, 1692 g (18 mol) of phenol, 60.6 g (0.3 mol) of dodecylthiol and 420 g (3 mol) of dihydroisophorone (3,3,5-trimethylcyclohexan-1 on) submitted at 28-3O ⁰ C. Into this solution at 28-3O ⁰ C 5h dry HCl gas is introduced. It is allowed to react for about 10 h at 28-3O ⁰ C. After 95% conversion of the ketone (GC-Kontrolla) are added to the reaction mixture 2.51 water and adjusted by addition of 45% NaOH solution has a pH of 6 a. The reaction mixture is stirred for one hour at 8O ⁰ C and then cooled to 25 ⁰ C.

The aqueous phase is decanted and washed dor remaining backlog with water at 8O ⁰ C. The resulting crude product is filtered off and extracted twice in each case with η-hexane and methylene chloride hot and filtered. The backwater is recrystallized twice from xylene.

Yield: 753g

Melting point: 209-211 ⁰ C.

Example A.3

Preparation of the diphenol of the formula (II)

In a return apparatus with stirrer, thermometer, reflux condenser and gas inlet tube, 564 g (6 mol) of phenol. 10.8 g (0.12 mol) of butanethiol and 140 g (1 mol) of dihydroisophorone (3,3,5-trimethyl-cyclohexan-i-one) at 3O ⁰ C submitted. At this temperature, 44 g of 37% HCl are added. The reaction mixture is stirred at 28-3O ⁰ C for about 70 hours. After 95% conversion of the ketone (GC control) is added to the reaction mixture 21 and water and by addition of 45% NaOH solution, a pH of 6 a. The reaction mixture is stirred for one hour at 8O ⁰ C and then cooled to 25 ⁰ C. The aqueous phase is decanted off and the remaining residue is washed with water at 80.degree. The resulting crude product is filtered off and extracted twice in each case with η-hexane and toluene hot and filtered at 30 ° C.

Yield: 253g

Melting point: 205-208 ° C

Example A.4

Preparation of the diphenol of the formula (I b), (R ¹ , R ² = CH ₃ )

In a stirred apparatus with stirrer, thermometer, reflux condenser and gas inlet tube 2196 g (18 mol) of 2,6-dimothylphenol, 38.2 g (0.36 mol) of β-mercaptopropionic acid and 420g (3 mol) of dihydroisophorone (3,3,5-trimethylcyclohexane -1-one) at 35 ⁰ C. Dry HCl gas is introduced into this solution at 35 ^° C. for 5 hours. It is allowed to react for about 10h at 30-35 ⁰ C. After 95% conversion of the ketone (GC control) is added to the reaction mixture 2.51 of water and by addition of 45% NaOH solution has a pH of 6 a. The reaction mixture is stirred for one hour at 8O ⁰ C and then cooled to room temperature. The aqueous phase is decanted and washed vcrbloibende residue with water at 6O ⁰ C. The resulting crude product is filtered off and extracted three times with η-hexane hot and filtered.

Yield: 856g

Melting point: 236-238 ⁰ C.

Example A.5

Preparation of diphenols of the formula (III)

Analogously to Example A2, 3 moles of 3,3-dimethylcyclohexanone are used instead of 3 mols of dihydroisophorone. The product had a melting point of 199-201 ⁰ C.

In the following examples relating to the preparation of polycarbonates, the relative viscosity is measured on 0.5% strength by weight solutions of the polycarbonates in CH ₂ Cl ₂ .

The glass transition temperature or glass transition temperature is measured by Differential Scanning Calorimetry (DSC).

Example B. 1

31.0 g (0.1 mol) of the diphenol according to Example (A. 1), 33.6 g (0.6 mol) of KOH and 560 g of water are dissolved in an inert gas atmosphere with stirring. Then a solution of 0.188 g of phenol in 560 ml of methylene chloride is added. 13 to 14 and 21 to 25 ⁰ C 19,8g (0,2MoI) was introduced phosgene at a pH in the well-stirred solution. Thereafter, 0.1 ml of ethylpyridine is added and stirred for 45 minutes. The bisphenolate-free aqueous phase is separated off, the organic phase, after acidification with phosphoric acid, washed neutral with water and freed from the solvent. The polycarbonate showed a relative solution viscosity of 1.259.

The glass transition temperature of the polymer was determined to be 233 ^° C. (DSC).

Example B.2

68.4 g (0.3 mol) of bisphenol A (2,2-bis- (4-hydroxyphenyl) -propane, 217, Og (0.7 mol) of diphenol according to Example (A. 1), 336.6 g (6 mol) of KOH and 2,700 g of water are dissolved in an inert gas atmosphere with stirring. Then add a solution of 1.88 g of phenol in 2500 ml of methylene chloride. into the well stirred solution at pH 13 to 14 and 21 to 25 ⁰ g C198 ( 1 ml of ethylpiperidine is then added and the mixture is stirred for a further 45 minutes, the bisphenolate-free aqueous phase is separated off and the organic phase, after acidification with phosphoric acid, is washed neutral with water and freed from solvent The polycarbonate showed a relative solution viscosity of 1.336

The glass transition temperature of the polymer was determined to be 212 ^° C. (DSC).

Example B.3

As in Example B.2, a mixture of 114 g (0.5 mol) of bisphenol A and 155 g (0.5 mol) of diphenol according to Example (A. 1) was converted to the polycarbonate.

The polycarbonate showed a relative solution viscosity of 1.368.

The glass transition temperature of the polymer was determined to be 195 ^° C. (DSC).

Example B.4

In Example B. 2, a mixture of 159.6 g (0.7 mol) of bisphenol A and 93 g (0.3 mol) of diphenol according to Example (A. 3) was converted to the polycarbonate.

The polycarbonate showed a relative solution viscosity of 1.437.

The glass transition temperature of the polymer was determined to be 18O ⁰ C (DSC).

Example B.5

31.0 g (0.1 mol) of diphenol according to Example (A.3), 24.0 g (0.6 mol) of NaOH and 270 g of water are dissolved in an inert gas atmosphere with stirring. Then a solution of 0.309 g of 4- (1,1,3,3-tetramethylbutyl) phenol in 250 ml of methylene chloride is added.

13 to 14 and 21 to 25 ⁰ C 19,8g (0,2MoI) was introduced phosgene at a pH in the well-stirred solution. Thereafter, 0.1 ml of ethylpiperidine is added and 45 min. touched. The bisphenolate-free aqueous phase is separated off, the organic phase, after acidification with phosphoric acid, washed neutral with water and freed from the solvent. The polycarbonate showed a relative solution viscosity of 1.314.

The glass transition temperature of the polymer was determined to be 234 ^° C. (DSC).

To estimate the UV resistance of the new polycarbonates, the primary radical formation on UV irradiation with a mercury vapor lamp (edge filter 305 nm) was determined in comparison to a polycarbonate based on 2,2-bis (4-hydroxyphenyl) propane. It was found that the polycarbonate according to Example B1 has a lower primary radical formation rate and therefore a higher UV resistance.

Example B.6

148.2 g (0.65 mol) of 2,2-bis- (4-hydroxyphenyl) -propane, 108.5 g (0.35 mol) of diphenol according to Example (A. 1), 336.6 g (6 mol) of KOH and 2700 g of water ^ dissolved in an inert gas atmosphere with stirring. A solution of 8.86 g of 4- (1,1,3,3-tetramethyl-Bu'.y-U-phenol in 2,500 ml of methylene chloride is then added, and 198 g of the well-stirred solution are added at pH 13-14 and 21-25 ° C. 1 ml of ethylpiperidine is added and the mixture is stirred for a further 45 minutes, the bisphenolate-free aqueous phase is separated off, the organic phase, after acidification with phosphoric acid, is washed neutral with water and freed from the solvent.The polycarbonate had a relative solution viscosity of 1, 20th

Example B.7

3,875 kg (12.5 mol) of bisphenol according to Example (A.2) are dissolved in 6.675 kg of 45% NaOH and 3Ol of water in an inert gas atmosphere with stirring. Then 9.431 of methylene chloride, 11.31 of chlorobenzene and 23.5 g of phenol are added. In the well-stirred solution at pH 13-14 and 20-25 ⁰ C 2.475 kg of phosgene are introduced. After completion of the introduction, 12.5 ml of N-ethylpiperidine are added. One lets 45min. afterreact. The bisphenolate-free aqueous phase is separated off, the organic phase is acidified with phosphoric acid and then washed free of electrolyte and freed from the solvent, rel. Viscosity: 1.300 (ilastemperatur: 238 ^C C

Example B.8

15.5 g (0.05 mol) of bisphenol according to Example (A.3), 13.4 g (0.05 mol) of bis (4-hydroxyphenol) -cyclohoxan (bisphenol Z), 24.0 g (0.6 mol) of NaOH are dissolved in Dissolve 362 ml of water in an inert gas atmosphere with stirring. Then, 0.516 g of 4- (1,1,3,3-tetramethylbutyuphenol dissolved in 271 ml of methylene chloride are added. Into the well stirred solution are added at pH 13-14 and

2O-25 ° C introduced 19.8 g of phosgene. 5 minutes after completion of the introduction, 0.1 ml of N-ethylpiperidine is added. The mixture is left to react for 45 minutes. The bisphenolate-free aqueous phase is separated off, the organic phase is acidified with phosphoric acid, and then washed neutral and freed from the solvent, rel. Viscosity: 1,297 Ulastemperatur: 208 ⁰ C

Example B.9

15.5 g (0.05 mol of bisphenol according to Example (A. 1), 17.6 g (0.05 mol) of 4,4'-dihydroxytetraphenylmethane, 24.0 g (0.6 mol) of NaOH in 411 r.il of water in dissolved in an inert gas atmosphere with stirring, then 0.516 g of 4-0,1,3,3-tetramethylbutyl) phenol dissolved in 308 ml of methylene chloride are added. In the well-stirred solution at pH 13-14 and 20-25 ⁰ C initiated 19,8g phosgene. 5 minutes after completion of the introduction, 0.1 ml of N-ethylpiperidine is added. The mixture is allowed to react for 45 minutes. The bisphenolate-free aqueous phase is separated off, the organic phase is acidified with phosphoric acid and then washed neutral and freed from the solvent, rel. Viscosity: 1,218 Glass transition temperature: 212 ⁰ C

Example B. 10

18.3 g (0.05 mol) of bisphenol according to Example (A.4), 23.6 g (0.42 mol) of KOH are dissolved in 100 ml of water in an inert gas atmosphere with stirring. Then 100 ml of methylene chloride are added. In the well-stirred solution at pH 13-14 and initiated 20-25 ⁰ C. 17.3 g of phosgene. 5 minutes after completion of the introduction, 0.3 ml of N-ethylpiperidine is added. The mixture is allowed to react for 45 minutes. The bisphenolate-free aqueous phase is separated off, the organic phase is acidified with phosphoric acid and then washed neutral and freed from the solvent, rel. Viscosity: 1,310 Glass transition temperature: 214 ⁰ C

Example B. 11

29.6 g (0.1 mol) of bisphenol according to Example (A.5), 24.0 g (0.6 mol) of NaOH are dissolved in 370 ml of water in an inert gas atmosphere with stirring. Then 0.413 g of 4- (1,1,3,3-tetramethylbutyl) phenol dissolved in 277 ml of methylene chloride are added. In the well-stirred solution at pK 13-14 and 20-25 ⁰ C initiated 19,8g phosgene. 5 minutes after completion of the introduction, 0.1 ml of N-ethylpiperidine is added. The mixture is allowed to react for 45 minutes. The bisphenolate-free aqueous phase is separated off, the organic phase is acidified with phosphoric acid and then washed neutral and freed from the solvent.

rel. Viscosity: 1.370

Glass transition temperature: 193 ^° C.

Example B. 12

62.0 g (0.2 mol) of bisphenol according to Example (A. 1), 182.4 g (0.8 mol) of bisphenol A, 240 g (6 mol) of NaOH are dissolved in 2400 ml of water in an inert gas atmosphere with stirring. Then 6.603 g of 4- (1,1,3,3-tetramethylbutyl) phenol dissolved in 2400 ml of methylene chloride are added. 13-14 and 20-25 ⁰ C198g phosgene are introduced at pH into the thoroughly stirred solution. 5 minutes after completion of the introduction, 1 ml of N-ethylpiperidine is added. The mixture is allowed to react for 45 minutes. The bisphenolate-free aqueous phase is separated off, the organic phase is acidified with phosphoric acid and then washed neutral and freed from the solvent, rel. Viscosity: 1,298 Glass transition temperature: 172 ⁰ C

Example B. 13

170.5 g (0.55 mol) of bisphenol according to Example (A.3), 102.6 g (04.5 mol) of bisphenol A, 240 g (6 mol) of NaOH are dissolved in 2400 ml of water in an inert gas atmosphere with stirring. Then 5.158 g of 4- (1,1,3,3-tetramethylbutyl) phenol dissolved in 2400 ml of methylene chloride are added. In the well-stirred solution at pH 13-14 and 20-25 ⁰ C 198g phosgene are introduced.

5 minutes after completion of the introduction, 1 ml of N-ethylpiperidine is added. Allow to react for 45 min. The bisphenolate-free aqueous phase is separated off, the organic phase is acidified with phosphoric acid and then washed neutral and freed from the solvent.

rel. Viscosity: 1.302

Glass typing: 203 ⁰ C

Example B.14

108.5 g (0.35 mol) of bisphenol according to Example (A. 1), 148.2 g (0.65 mol) of bisphenol A, 240 g (6 mol) of NaOH are dissolved in 2400 ml of water in an inert gas atmosphere with stirring. Then 6.189 g of 4- (1,1,3,3-tetramethylbutyl) phenol dissolved in 2400 ml of methylene chloride are added. 13-14 and 20-25 ⁰ C198g phosgene are introduced at pH into the thoroughly stirred solution. 5 minutes after completion of the introduction, 1 ml of N-ethylpiporidine is added. One lets 45min. afterreact. The bisphenolate-free aqueous phase is separated off, the organic phase is acidified with phosphoric acid and then washed neutral and freed from the solvent, rel. Viscosity: 1,305 Glass transition temperature: 185 ⁰ C

Examples

From the copolycarbonate according to Example (B. 6) and from a bisphenol A homopolycarbonate with η ,,, = 1.20, compact discs with a diameter of 12 cm were produced on a Netstal injection molding machine (melt temperature 330 ° to 350 ° C.). The birefringence in the axial direction was checked by retardation measurements by using a conventional comparator using a polarizing microscope. The transparency was assessed visually, the glass transition temperature determined by DSC.

Material retardation T ₈ transparency

[nm / nm] [ ⁰ C]

Example B6 +13 185 yes

Bisphenol A

Polycarbonate +12 145 yes

Example D! Film production)

20s of the polycarbonate from Example B. 1 were dissolved in 200 ml of methylene chloride with constant stirring at 30 ° C, the solution thickened and then prepared by pouring onto a flat glass plate at 25 ° Ceinenfolie a thickness of 240pm.

This film was dried at 90 ^° C. under vacuum for 4 hours, and then the gas permeability through this film was measured.

Determination of gas permeability (permeation) of polymer membranes

The passage of a gas through a dense polymer membrane is described by a solution-diffusion process. The characteristic constant for this process is the permeation coefficient P, which indicates which gas volume V passes through a film of known area F and thickness d at a given pressure difference Δρ in a given time t. For the stationary state it can be deduced from the differential equations of the permeation process:

^P < ¹ >

F · t · Δρ

In addition, the permeation depends on the temperature and the water content of the gas.

The measuring arrangement consists of a thermostated two-chamber system. One chamber is designed for receiving the default gas and the other for receiving the permeate. The chambers are separated by the polymer membrane to be measured.

Both chambers are evacuated to 10 " ³ mbar and the default chamber is then filled with gas The permeated gas (inert gases) then causes a pressure increase in the permeate chamber at a constant volume, which is controlled by a pressure sensor (Baratron from MKS) The pressure rise can be used to calculate V (for normal pressure and normal temperature), t is known, Δρ is set to 10 ⁵ Pa, taking into account the external air pressure, the membrane area F is known determined by means of a micrometer screw as a mean of 10 independent thickness measurements distributed over the membrane surface.

From these quantities, the permeation coefficient P according to (1) is to be determined in the dimension

i " cm ³ (NTP) mm 1 [m ² * 24h 10 ⁶ Pa J

being based on a membrane thickness of 1 mm.

Further measuring parameters are:

Temperature: 25 ± 1 ° C rel. Gas humidity: 0%

Result: Permeation coefficient for O ₂ : 280.8 for N ₂ : 84.5

for CO ₂ : 2174.0 for CH ₄ : 149.4

The film was still dimensionally stable at 180 ° C.

D.2 (comparative example)

As in Example D. 1, a film of bisphenol A polycarbonate having a relative viscosity of 1.28 (thickness: 154 nm) was measured and measured.

Result: permeation coefficient

for O ₂ : 72.0 for N ₂ : 366.0 for CO ₂ : 35.0 for CH ₄ : 27.0

At 18O ⁰ C, this film was no longer dimensionally stable.

Example D. 3

As described in Example D. 1, from 20 g of the polycarbonate from Example B. 12 a film of thickness 92pm is prepared and then measured the gas permeability.

Example D.4

As described in Example D. 1, from 20 g of the polycarbonate from Example B. 13 a film of thickness 95μηι prepared and then measured the gas permeability.

Example D.5

As described in Example D. 1, from 20 g of the polycarbonate from Boispiel B. 14 a film of thickness 89.7 .mu.m prepared and then measured the gas permeability.

Example D.6

The polycarbonate from Example B. 7 is melted in an extruder (temperature: 360-37O ⁰ C) and extruded through slot dies into a film having a thickness of 163 mm and then measured the gas permeability.

Example D.7

31 g (0.1 mol) of bisphenol A 1.24 g (0.6 mol) of NaOH are dissolved in 270 ml of water in an inert gas atmosphere with stirring. Then 250 ml of methylene chloride are added. 19.8 g of phosgene are introduced into the well-stirred solution at pH 13-14 and 20-25 ° C. 5 minutes after completion of the introduction, 0.1 ml of N-ethylpipeilidine is added and the mixture is left to react for 45 minutes The phase is separated, the organic phase is acidified with phosphoric acid, and then washed neutral.From the concentrated solution in methylene chloride was poured a film that was clearly transparent.GPC analysis: The molecular weight was measured based on calibration with bisphenol A polycarbonate. M _w = 246000, M _n = 38760

Results permeation words:

N, O ₂ Permeationsgase CO ₂ CH ₄ sample 23.9 109.2 634.9 30.2 D. 3 49.7 227.9 1 629.5 64.3 D.4 33.6 138.8 828.1 46.8 D.5 78.2 400.5 2 555.0 n.d. D.6 nb .: not determined

D. 8 (composite line)

The films prepared according to D. 1 and D. 2 were placed on each other after evaporation of the solvent and pressed at 235 ° C and a pressure of about 234 bar for 4 minutes to form a film having a thickness of about 307 pm.

The gas permeability of the composite film was measured as described in D. 1.

Result: Permeation coefficient for O ₂ : 208.3 for CO ₂ : 1209.4 for CH ₄ : 77.1

This composite line was also stable at 180 ° C.

Example D.9

Compound line of polycarbonate according to Example B. 14 and Polymethylmethycrylat A polymethylmethacrylate (PMMA) film with a thickness of 130pm and a film of polycarbonate B. 14 of thickness 131 μιη be at 160 "C after 30 seconds preheating under a pressure of 200 bar The gas permeabilities of the composite film were measured as described in Example D. 1.

Example D.10

Composite film of polycarbonate according to Example B. 14 and polystyrene

A polystyrene film (polystyrene N168 from BASF AG) with a thickness of 78 pm and a film of the polycarbonate B. 14 to the thickness of 101 pm are ⁰ C nai.ii 30 seconds pre-heating under a pressure of 200 bar for 30 seconds at 16O to a composite film of thickness 168pm pressed. The gas permeabilities of the composite film were measured as described in Example D. 1.

Results permeation values:

Permeationsgaso

sample N ₂ O ₂ CO ₂ CH ₄ D.9 0.7 * 4.5 20.3 0.42 · D. 10 18.0 102.9 488.5 25.6

Since in this composite film a very small increase in pressure after gas presetting in a measuring cell showed, the Permeatlonswert was determined from the Pormeat after 3 days Permalionszeit.

Claims (1)

claims: 1. Process for the preparation of dihydroxydiphenylcycloalkanes of the formula (I) ,1 wherein R ¹ and R ^{2 are} independently hydrogen, halogen, C ₁ -C ₈ alkyl, C ₅ -C ₆ cycloalkyl, C ₆ -C ₁₀ aryl and C ₇ -C ₁₂ aralkyl, m an integer from 4 to 7 R ³ and R ⁴ for each X are individually selectable, independently of one another hydrogen, C ₁ -C ₆ -alkyl and X is carbon with the proviso that on at least one atom XR ³ and R ^{4 are} simultaneously alkyl. characterized in that phenols of the formula (V)