DD297605A5 - COMPOSITE FOILS WITH POLYCARBONATES - Google Patents

Abstract

The invention relates to composite films of a polycarbonate film and a film of another plastic, wherein the polycarbonate film consists of a high molecular weight, thermoplastic, aromatic polycarbonate having Mw (weight average molecular weights) of at least 10,000, the bifunctional carbonate structural units of the formula (I a), wherein R1 and R 2 independently of one another are hydrogen, halogen, C 1 -C 8 -alkyl, C 5 -C 6 -cycloalkyl, C 6 -C 10 -aryl and C 7 -C 12 -aralkyl, m is an integer from 4 to 7, R 3 and R 4 are individually selectable for each X, independent of one another each other is hydrogen, C1-C6-alkyl and X is carbon, with the formula that at least one atom X R3 and R4 are simultaneously alkyl, in amounts of 100 mol% to 2 *, each based on the total amount of 100 mol% of contains difunctional carbonate structural units in the polycarbonate. Formula (I a) {composite film; polycarbonate; Plastic; Carbonate structure, thermoplastic, aromatic}

Description

R ¹ and R ² independently of one another are hydrogen, halogen, C ₁ -C ₈ -alkyl, C ₁ -C ₆ -cycloalkyl, and C 7 -C 2 -aralkyl,

m is an integer from 4 to 7,

R ³ and R ^{4 are} individually selectable for each X, independently of one another hydrogen, C 1 -C ₆ -alkyl and

X carbon mean

with the proviso that on at least one atom XR ³ and R ^{4 are} simultaneously alkyl, in amounts of 100 mol% to 2 mol%, based in each case on the total amount of 100 mol% of bifunctional carbonate structural units in the polycarbonate.

Field of application of the invention The invention relates to composite films of a polycarbonate film and a film of another plastic. Characteristic of the known state of the art

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, WO 8000348, 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.

Object of the invention

The aim of the invention is the enrichment of the prior art by composite films with a polycarbonate component which has improved properties, in particular a high heat resistance.

Explanation of the essence of the invention The invention relates to composite films of a polycarbonate film and a film of another plastic. The polycarbonate film is based on a high molecular weight, thermoplastic, aromatic polycarbonate consisting of diphenols

which is prepared as diphenols-dihydroxydiphenylcycloalkanes of the formula (I)

(D,

R ¹ 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 -aryl, preferably phenyl, and C ₁ -C 12 -aralkyl, 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 , individually selectable for each X, independently of one another denote hydrogen or C 1 -C ₆ -alkyl and X signify carbon,

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

In the case of the new diphenols, preference is given to X, in particular only to one atom X, R ³ and R ⁴ simultaneously being alkyl on 1-2 atoms. Preferred alkyl is methyl; the X atoms in α position relative to the di-phenyl-substituted C atom (CD are preferably not dialkyl-substituted, whereas alkyl disubstitution in the β position relative to C-1 is preferred Dialkylsubstituted in the β-position, and an X atom in the β'-position monoalkylsubstituiert.

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

hohQ

(III) and

(IV),

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

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

R ¹

(V)

and ketones of the formula (VI)

are prepared, wherein in the formulas (V) and (VI) X, R ¹ , R ² , 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 available (see

for example, for cresols and xylenols, Ulimann's Encyclopedia of Industrial Chemistry 4. reworked and expanded

Edition Volume 15, pages 61-77, Verlag Chemie Weinheim-New York 1978; for chlorophenols, Ulimanns encyclopedia of

Technical Chemistry, 4th Edition, Verlag Chemie, 1975, Volume 9, pages 573-582; and for alkylphenols, Ullmanns Encyklopadie der technischen Chemie, 4th Edition, 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 Handbook of Organic Chemistry 7, Vol Edition, Springer-Verlag, Berlin, 1925 and the corresponding supplementary volumes 1 to 4, and J. Am. Chem. Soc. Vol. 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, described. Examples of known ketones of the formula (VI) are:

3,3-dimethylcyclopentanone, 3,3-dimethylcyclohexanone, 4,4-dimethycyclohexanone, 3-ethyl-3-methylcyclopentanone, 2,3,3-trimethylcyclopentanone, 3,3,4-trimethylcyclopentanone, 3,3-dimethylcycloheptanone, 4, 4-dimethylcycloheptanone, 3-ethyl-3-methylcyclohexanone, 4-ethyl-4-methylcyclohexanone, 2,3,3-trimethylcyclohexanone, 2,4,4-trimethylcyclohexanone, 3,3,4-trimethylcyclohexanone, 3,3, 5-trimethylcyclohexanone, 3,4,4-trimethylcyclohexanone, 2,3,3,4-tetramethylcyclopentanone,

S.S.-trimethylcycloheptanone, 3,5,5-trimethylcycloheptanone, 5-ethyl-2,5-dimethylcycloheptanone,

2,3,3,5-tetramethylcyclohephenyl, 2,3,5,5-tetramethylcycloheptanone, 3,3,5,5-tetramethylcycloheptanone, 4-ethyl-2,3,4-trimethylcyclopentanone, S-ethyl-isopropyl S-methylcyclopentanone, 4 sec. Butyl 3,3-dimethylcyclopentanone, 2-isopropyl-3,3,4-trimethylcyclopentanone, S-ethyl-1-isopropyl-S-methylcyclohexanone, 4-ethyl-3-isopropyl-4-methylcyclohexanone, 3 sec. Butyl-4,4-dimethylcyclohexanone, 2-butyl-3,3,4-trimethylcyclopentanone, 2-butyl-3,3,4-trimethylcyclohexanone, 4-butyl-3,3,5-trimethylcyclohexanone, 3-isohexyl-3-one methylcyclohexanonund

S.S.S-Trimethylcyclooctanon. Examples of preferred ketones are

CH ₃

CH ₃

⁰ⁱⁱ 3

For bisphenol preparation, in general from 2 to 10 mol, preferably from 2.5 to 6 mol, of phenol (V) per mole of ketone (VI),

used. 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 15O ⁰ 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, boron trifluoride, 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. The use of acidic ion exchangers is also possible. Furthermore, the reaction by addition of co-catalysts such as Ci-C ^ alkyl mercaptans, hydrogen sulfide, Thiophenols, thioacids and dialkyl sulfides are preferred in amounts of 0.01-0.4 mol / mol of ketone, in particular

0.05-0.2 moles / mole of ketone are accelerated.

The condensation can be carried out without solvent or in the presence of an inert solvent (eg 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 the latter is advantageous for achieving good conversions in any case when 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 high molecular weight polycarbonates of the diphenols of the formula (I), optionally 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 process for the preparation of high molecular weight thermoplastic aromatic polycarbonates from diphenols, optionally chain terminators and optionally branching agents according to the known methods of polycarbonate production, preferably by two-phase interfacial polycondensation is that of diphenols those of formula (I) in amounts of 100 mol% to 2 mol%, preferably in amounts of from 100 mol% to 5 mol% and in particular in amounts of from 100 mol% to 10 mol%, and very particularly from 100 mol% to 20 mol%, based in each case on the total molar amount of diphenols used , used.

When used as branching, if used, in 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-tris (4-hydroxyphenyl) ethane,

Tri- (4-hydroxyphenyl) phenylmethane,

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

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

2,6-bis- (2-hydroxy-5'-methyl-benzyl) -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

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 terminator 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

ho- ^ -y (viii) _f

wherein R represents branched C ₈ and / or Cg-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 used in general in amounts of 0.5 to 10, preferably 1.5 to 8, mol%, based on diphenols.

The polycarbonates 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 chain terminators, for. example, the formula (VIII) are added. Then, in the presence of an inert, preferred polycarbonate is solved, reacted organic phase with phosgene by the method of interfacial condensation. the reaction temperature is between ⁰ ° C and 40 ° C. the optionally used 0.05 to 2 mol% of branching agents can be pre-packed with either the diphenols in the aqueous alkaline phase be added 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); Similarly, when using chloroformates the amount of phosgene can be reduced accordingly in a known manner.

Suitable organic solvents for dissolving the chain terminators and, where appropriate, the branching agents and the chlorocarbonic acid esters are, for example, methylene chloride, chlorobromone, 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.

The organic phase used for the interfacial polycondensation is, for example, methylene chloride, chlorobenzene and mixtures of methylene chloride and chlorobenzene.

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

The formation of the polycarbonates by interfacial polycondensation can be accelerated usually by catalysts such as tertiary amines, in particular tertiary aliphatic amines such as tributylamine or triethylamine; the catalysts can be used in amounts of from 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 can be separated in a known manner.

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

The polycarbonates obtainable by the process described 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. As far 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 polycarbonates according to the invention 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 150000 g / mol are preferred. The polycarbonates of the invention may be linear or branched, they are homopolycarbonates or copolycarbonates

based on the diphenols of the formula (I).

The present invention relates to high molecular weight thermoplastic aromatic polycarbonates having Mw (weight average molecular weights) of at least 10,000, preferably from 10,000 to 300,000, which are present as films. The polycarbonate film accordingly consists of a high molecular weight, thermoplastic, aromatic polycarbonate having Mw (weight average molecular weights) of at least 10,000 , preferably from 10,000 to 300,000 g / mol, of the bifunctional carbonate structural units of the formula (Ia)

,1

(La),

X, R ', R *, 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 especially in amounts of from 100 mol% to 10 mol% and very particularly from 100 mol% to 20 mol%, based in each case on the total amount of 10 mol% of difunctional carbonate structural units in the polycarbonate.

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

(Vila)

that is, OMol% (inclusive) to 98 mole% inclusive, preferably, OMol% to 95 mole%, and especially, OMol% to 90 mole%, and more particularly, preferably, OMol% to 80 mole% based on the total amount (of 100 mol%) of difunctional carbonate structural units in the polycarbonate.

It has now surprisingly been found that the incorporation of the diphenols of formula (I) 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 more particularly for the polycarbonates based on the diphenols (Ib)

(Ib)

R 'and R ² independently of one another have the meaning given for formula (I) and are particularly preferably hydrogen.

Thus, preferably polycarbonates in which in the structural units of the formula (I a) m = 4 or 5 and especially those with structural units of the formula (Ic)

(Ic)

R ¹ and R ^{2 have} the meaning given for formula (Ia), but are particularly preferably hydrogen.

These polycarbonates based on the diphenols of the formula (I b), in which in particular R '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 described is done 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 before or after their processing additives customary for thermoplastic polycarbonates such as stabilizers, mold release agents, pigments, flame retardants, antistatic agents, fillers and reinforcing agents are added in the usual amounts.

Specifically, for example, carbon black, graphite, diatomaceous earth, kaolin, clays, CaF ₂ , CaCO ₃ , aluminum oxides, glass fibers, barium sulfate and inorganic pigments can be added both as fillers and as a nucleating agent and as mold release agents such as glycerol stearates, pentaerythritol tetrastearate and trimethylolpropane tristearate.

In particular, films can be made from the high molecular weight aromatic polycarbonates of the invention. The films have preferred thicknesses between 1 and 1500μηι, in particular preferred thicknesses between 10 and 900μπι.

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

The films can be prepared according to known methods for film production, e.g. Example by extrusion of a polymer melt through a slot die, by blowing on a film blowing machine, 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 between room temperature and a temperature at which the viscosity of the polymer melt is not yet too low, generally up to about 370 ⁰ C, drawn on known devices.

The film production by casting the polycarbonate solutions, for example, by pouring concentrated solutions of the polycarbonates in a suitable solvent on flat surfaces and then evaporates the solvent at a temperature control of the flat surfaces between room temperature and 150 ° C. It is also possible to apply the concentrated solutions of the polycarbonates to liquids which have a higher density than the concentrated solutions, are incompatible with the solvent used and do not dissolve the polycarbonate, and after spreading the films by evaporation of the solvent used for the polycarbonate and possibly also the liquid of higher density.

The films have a particularly high heat resistance and are permeable to many gases while still good selectivity. They can therefore be used advantageously as membranes for gas permeation.

It is possible to use these slides on their own.

It is of course also possible according to the invention to produce composite foils with other plastic foils according to the invention, with all known foils being suitable as partners in principle, depending on the desired application and end property of the composite foil. For example, a composite of two or more films can be produced by stacking the individual films, including the polycarbonate film of the invention, under pressure at suitable temperatures determined by the softening points of the individual films. It is also possible to use the known film coextrusion process.

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 non-cooled 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. A pressure between 2 and 500bar 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 be flat, hollow bodies of different geometries form - cylindrical, spherical, tubular - or even hollow fibers. Such moldings can be prepared by the methods known 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 therefore also possible to achieve gas-impermeable composite films which have a better heat distortion resistance than the prior art, or one can obtain heat-resistant, gas-permeable composite films, depending on the choice of the composite 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) amorphous thermoplastics, preferably those having a glass transition temperature of more than 40 ⁰ C, in particular from 60 ° C to

22O ⁰ C, and b 2) partially crystalline thermoplastics, preferably those having a melting temperature of more than 6O ⁰ C, in particular from 8O ⁰ C to 400 ⁰ C.

Elastomers for the component b) are b3) are those which have a glass transition temperature of below ⁰ C, preferably below -10 ° C and especially from -15 ⁰ C to -140 ° C.

Examples of amorphous thermoplastics b 1) are amorphous polymers from the class of polycarbonates, polyamides, polyolefins, polysulfones, polyketones, thermoplastic vinyl polymers such as polymethylacrylates or homopolymers of vinylaromatics, copolymers of vinylaromatics 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, polyarylene sulfides and the partially crystalline representatives of the above under b 1) subsummioilen thermoplastics.

Examples of elastomers b3) are a wide variety of 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 acid esters, elastic polyurethanes where not as thermoplastics and b 1) or b 2) subsumed and elastic polycarbonate-polyether block copolymers. Amorphous thermoplastics b 1) are in particular polycarbonates (except for 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 polycarbonates are between 10,000 and 300,000, preferably between 12,000 and 150,000.

The thermoplastic polycarbonates can be used both individually and in 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-hydroxymethylcyclohexane,

The molecular weights (Mw) of these polyalkylene terephthalates are between 10,000 and 80,000. The polyalkylene terephthalates can be obtained by known methods from, for example, terephthalic acid dialkyl ester and the corresponding diol by transesterification (see, for example, U.S. Patents 2,647,885, 2,643,989, 2,353,408,257,886, 2,674,244,2901466). 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 are suitable. Components. Also suitable are partially crystalline polyamides whose acid component is, in particular, completely or partially adipic acid or caprolactam 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 its diamine component wholly or partially in particular of m-unc / 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 exist and whose compositions are known in principle from the prior art (see, for example, Encyclopedie of polymers, Vol. 11, p.315 ff.).

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 hexamethylenediamines ^ decamethylenediamine, 2,2,4- and 2,4,4, -Trimethylhexamethylendiamin, m- or p-xylylenediamine, bis (4-aminocyclohexyl ) -methane, mixtures of 4,4'- and 2,2'-diaminodicyclohexylmethanes, 2,2-bis (4-aminocyclohexyl) -propane, 3,3'-dimethyl-4,4'-diaminodicyclohexylmethane, S-aminoethyl -S.O.S-trimethylcyclohexylamine, 2,5-bis (aminomethyl) norbornane, 2,6-bis (aminomethyl) norbornane, M-diamino-methylcyclohexane and 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 abovementioned diamines and / or dicarboxylic acids.

Also included are amorphous copolyamides prepared with the co-use of co-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 which are selected from isophthalic acid, hexamethylenediamine and further 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 derived from isophthalic acid,

4,4'-diamino-di-cyclohexylmethane and ω-caprolactam are available, those obtainable from isophthalic acid, 3,3-dimethyl-4,4'-diamino-dicyclohexylmethane and ω-laurolactam, and those derived from terephthalic acid and the isomer mixture of 2,2,4- and 2,4,4-trimethylhexamethylenediamine are available. Instead of the pure 4,4'-diaminodicyclohexylmethane, it is also possible to use mixtures of the positionally isomeric diaminodicyclohexylmethanes which are composed

70 to 99 mol% of the 4,4'-diaminoisomer 1 to 30 mol% of the 2,4'-diaminoisomer 0 to 2 mol% of the 2,2'-diamino isomer

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

Suitable thermoplastic polyamides 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 also known from the prior art (see, for example, Ulimann, Enzyklopädie d.

Technical Chemistry, Volume 19, p.50).

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

J η

where R ₁ to R ₄ may be identical or different and denote C, -C ₆ alkyl, phenyl or hydrogen. The polyarylene sulfides may also contain diphenyl units. Polyarylene sulfides and their preparation are known (see for example US-PS 3354129 and EP-A 0171 021).

Further preferred other thermoplastics b) are thermoplastic polyarylene sulfones.

Suitable polyarylene sulfones have weight average molecular weights 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 polyarylene sulfones obtainable by known processes from 4,4'-dichlorodiphenyl sulfone and a bisphenol, in particular 2,2-bis (4-hydroxyphenyl) propane, with Mw from 2000 to 200,000.

Polyarylene sulfones are known (see, for example, US Pat. No. 3,246,536, DE-AS 1794171, GBPS 1264900, US Pat. No. 3,641,207, EP-A-0038028, 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 thormoplasts b) are also known thermoplastic polyphenylene oxides, preferably poly (2,6-dialkyl-1-phenylene oxides) having molecular weights M w (weight average, measured by light scattering in chloroform) of from 2,000 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-PS 3306875).

Particularly suitable are poly [2,6-di (C _l -C ₄ alkyl) -1,4-phenylene oxides], z. For example, poly (2,6-dimethyl-1,4-phenylene oxide).

Preferred other thermal plates 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

-0-E-O-E ',

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

They can be prepared, for example, according to GB-PS 1078234 from Dialkalidiphenolaten the formula alkali-O-E-O-alkali and bis (haloaryl) ketones of the formula Hal-E'-Hal (with Hal = halogen). A suitable dialkalidiphenolate is

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

Preferred other thermoplastics b) are 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 which are suitable according to the invention are those of styrene, α-methylstyrene, acrylonitrile, methacrylonitrile, C 1 -C ₂ -cycloalkyl esters of (meth) acrylic acid, C 1 -C 6 -carboxylic acid vinyl esters, where the copolymers consist of mixtures of these vinyl Compounds are obtainable by known methods.

The homopolymers or copolymers should have intrinsic viscosities (Staudinger indices) of between 0.3 and 1.5 dl / g (measured at 23 ° C. in toluene in a known manner).

Suitable vinyl polymers are, for example, thermoplastic poly-C 1 -C 4 -alkyl methacrylates, for example those of the methyl, ethyl, propyl or butyl methacrylate, preferably of the methyl or ethyl methacrylate. Both homopolymers and copolymers of these methacrylic esters are to be understood as meaning. In addition, other, ethylenically unsaturated copolymerizable monomers such as (meth) acrylonitrile, (a-methyl) styrene, bromostyrene, vinyl acetate, acrylic acid-Ci-Ca-alkyl ester, (meth) acrylic acid, ethylene, propylene and N-vinylpyrrolidone in subordinate Be polymerized into amounts.

The inventively suitable thermoplastic poly-Cj-Cralkyl methacrylates are known from the literature or obtainable by literature methods.

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 present in proportions between 100 and 10 wt .-%, preferably between 90 to 20 wt .-%, particularly preferably between 80 to 30 wt .-%, containing by conventional methods such as radical polymerization in bulk, solution, Suspension or emulsion, but preferably obtained by free-radical emulsion polymerization in water.

Suitable graft polymers are formed by polymerization of the abovementioned vinylic or monomeric vinyl monomer mixtures in the presence of rubbers having glass transition temperatures <0 ° C., preferably <-20 ° C. 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, wherein vinyl monomer mixtures can be graft-polymerized simultaneously or successively. Suitable rubbers are preferably diene rubbers and acrylate rubbers.

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

Acrylate rubbers are, for example, crosslinked, particle-shaped emulsion polymers of C 1 -C 6 -alkyl acrylates, in particular C 1 -C 6 -alkyl acrylates, optionally in a mixture with up to 15% by weight of other, unsaturated monomers such as styrene, methyl methacrylate, butadiene, vinylmethyl ether, acrylonitrile, and of at least one polyfunctional crosslinking agents such as, for example, divinylbenzene, glycol bis-acrylates, bisacrylamides, triallyl phosphates, citric acid triallyl 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 having a core-shell structure are also 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 50 to 90 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-transparent rubbers (diene or alkyl acrylate rubbers) with gel contents> 80% by weight and average particle diameters (d 50) of 80 to 800 nm. Particularly suitable are industrially customary ABS polymers.

Mixtures of vinyl homopolymers and / or vinyl copolymers with graft polymers are also suitable. 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 are known or can be prepared by known methods (see, for example, US Patent 3,214,411, JH Saunders and KC Frisch, "Polyurethanes, Chemistry and Technology", VoI II, 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 the preparation of the oligoesters and polyesters are adipic acid, succinic acid, subecynic 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 oligomers or polyesters have a molecular weight of at least 600, a hydroxyl number of about 25 to 190, preferably about 40 to 150, an acid number of about 0.5 to 2 and a water content of about 0, 01 to 0.2%. Oligoesters or polyesters are also oligomeric or polymeric lactones, such as, for example, oligo-caprolactone or polycaprolactone, and aliphatic polycarbonates, such as, for example, polybutanediol (1,4) carbonate or polyhexanediol (1,6) carbonate.

A particularly suitable oligoorest that can be used as the 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 olioethers 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 obtained by extraction of the chloride from the luocyanate in hot, aqueous methanol solution or by liberation of the chloride on hydrolysis with water and titration. Extract with standard silver nitrate solution determined to obtain the existing chloride ion concentration.

Other diisocyanates can also be used to prepare the thermoplastic polyurethanes, for example the Diisocyanates of ethylene, ethylidene, propylene, butylene, cyclopentylene-1,3, cyclohexylene-1,4, cyclohexylene-1,2, des

2,4-tolylene, 2,6-tolylene, p-phenylene, n-phenylene, xylene, 1,4-naphthylene, 1,5-naphthylone, dos4,4'-diphenylene, 2, 2-diphenylpropane-4,4'-diisocyanate, the azobenzene-4,4'-diisocyanate, the diphenylsulfone-4,4'-diisocyanate, the dichlorohexanemethylene diisocyanate, the pentamethylene diisocyanate, the hexamethylene diisocyanate, the 1-chlorobenzene 2,4-diisocyanate, furfuryl diisocyanate, dicyclohexylmethane diisocyanate, isophorone diisocyanate,

Diphenylethane c'iisocyanate and bis (isocyanatophenyl) ether of ethylene glycol, butanediol, etc. As chain extenders it is possible to use organic difunctional compounds which are active, with isocyanates

reactive, hydrogen containing, for example, diols, hydroxycarboxylic acids, dicarboxylic acids, diamines and alkanolamines and water.

As such, for example, ethylene, propylene, butylene glycol, 1,4-butanediol, butanediol, butynediol, xylylene glycol, Amylene glycol, 1,4-phenylene-bis-.beta.-hydroxyethyl ether, 1,3-phenylene-bis-.beta.-hydroxyethyl ether, bis (hydroxy-methyl)

cyclohexane), hexanediol, adipic acid, hydroxycaproic acid, thiodiglycol, ethylene diamine, propylene, butylene, hexamethylene,

Cyclohexylene, phenylene, toluylene, xylylenediamine, diaminodicyclohexylmethane, isophoronediamine, 3,3'-dichlorobenzidine,

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 moves in the

Range 1: 1 to 1: S0, preferably 1 :?. until 1:30. In addition to difunctional chain extenders can also be used in minor amounts up to about 5 mol%, based on moles

used bifunctional chain extenders, trifunctional or more than trifunctional chain extenders.

Such trifunctional or more than trifunctional chain extenders are, for example, glycerol, trimethylolpropane, Hexanetriol, pentaerythritol and triethanolamine. Monofunctional components, for example butanol, can also be used to prepare the thermoplastic polyurethanes

be used.

The diisocyanates, oligoesters, polyesters, polyethers mentioned as building blocks for the thermoplastic polyurethanes, Chain extenders and monofunctional components are either known from the literature or from literature Method available. The known preparation of the polyurethanes can be carried out, for example, as follows: Thus, for example, the oligo or polyester, the organic diisocyanates and the chain extenders for themselves

preferably heated to a temperature of about 50 to 22O ⁰ C and then mixed. Preferably, the oligo- or

First heated individually polyester, then mixed with the chain extenders and the resulting mixture with the preheated Isocyanate mixed. The mixing of the starting components to make the polyurethanes can be accomplished 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 to 0.05% by weight, based on

Ester), citric acid or the like may be added to reduce the rate of the reaction. To increase the Reaction rate, suitable catalysts, such. tertiary amines referred to in US Pat. No. 2,729,618

will be used.

Other preferred thermoplastics are also known as "LC polymers." LC polymers are polymers which

can form liquid crystalline melts. Such polymers, which are also referred to as "thermotropic", are well known (see for example EP-OS 0131848, EP-OS 0132637 and EP-OS 0134959) in the cited references is further literature and also described the determination of the liquid crystalline state of polymer melts ,

"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 Hydroxy benzoic acid, diphenols,

Carbonic acid and optionally aromatic dicarboxylic acids (EP-OS 0132 637) 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'-Dihydroxydiphenylsulfid (EP-OS 0134959).

The LC polymers have a persistence length at room temperature between 18 and 1300 A, preferably between 25 and 300 A,

especially between 25 and 150A.

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, e.g., P.J. Flory, "Principles of Polymer Chemistry", Cornell Univ.

Ithaca, New York) and half of Kuhn's stride. Persistence length can vary with different methods

diluted solutions, e.g. by light scattering and small angle X-ray measurements. After suitable preparation, the persistence length can also be determined with the aid of the neutron small-angle scattering in the solid state. Further theoretical and experimental methods are e.g. in J.H.Wenndorff in "Liquid Crystalline Order in Polymers", e.g.

A. Blumstein, Academic Press 1978, p. 16ff. as well as in the "S. M. Aharoni, Macromolecules 19, (1986), p.429 et seq References described. Preferred other thermoplastics are also aromatic polyester carbonates. Aromatic polyesters and polyester carbonates which can be used according to the invention as thermoplastic b) are at least one

aromatic bisphenol, e.g. of formula (VII), from at least one aromatic dicarboxylic acid and optionally from

Carbonic acid. Suitable aromatic dicarboxylic acids are, for example, orthophthalic acid, terephthalic acid, Isophthalic acid, tert-butylisophthalic acid, S.S'-diphenyldicarboxylic acid ^^ '- diphenyldicarboxylic acid,

4,4'-benzophenonedicarboxylic acid, 3,4'-benzophenonedicarboxylic acid, 4,4'-diphenyletherdicarboxylic acid, 4,4'-diphenylsulfonedicarboxylic acid, 2,2-bis (4-carboxyphenyl) -propane, trimethyl-3-phenylindai.-4 , 5'-dicarboxylic 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 methods known in the literature for polyester or polyester carbonate production, such as, for example, US Pat. B. by homogeneous solution, by melt transesterification and Zweipha.sengrenzflächenverfahren. Preference is given to using melt-remelting processes and in particular the two-phase interfacial process.

Melt transesterification processes (acetate process and phenyl ester process) are described, for example, in US Pat. Nos. 3,494,885, 4,386,186, 4,666,185, 4,680,371 and 4,680,372, EP-A 26120, 26121, 26684, 28030, 398, 998, 45, 16, 92, 79, 770, 14, 487, 1987; 240301 and DE-A 1495626,2232977 described. The two-phase interface process is described, for example, in EP-A 68014.88322, 134898, 151750, 1882189, 219708, 272426, DE-OS 2940024, 3007934, 3440020 and in Polymer Reviews, Volume 10, "Condensation Polymers by Interfacial and Solution Methods". , Paul W. Morgan, lnterclean Publishers, New York 1965, Chapter VIII, p. 325, Polyester.

In the acetate process, generally bisphenol diacetate or, in the phenyl ester process, bisphenol, aromatic dicarboxylic acid or diphenyl ester of the aromatic dicarboxylic acid and, optionally, diphenyl carbonate with the elimination of phenol and optionally CCy cleavage are reacted to form the polyester or polyester carbonate. In the two-phase interfacial process, starting materials for the preparation of polyesters and polyestercarbonates are 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, insofar as they are elastic in nature, styrene, butadiene block copolymers, which may be partially hydrogenated (for example Kraton G ^e of Shell), the 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 composite films may 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.

In the following examples, 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 A.1

Preparation of the diphenol of the formula (II)

In an 11-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 saturated at 28 to 30 ° C with dry HCl gas , To this solution, a solution of 1.5 moles (210 g) of dihydroisophorone (3,3, b-trimethyl-cyclohexon-1-one) and 1.5 moles (151 g) of phenol are added dropwise within 3 hours, with further HCl gas is passed into the reaction solution. After the end of the dropping, HCl gas is introduced for a further 5 hours. It is allowed to react 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: 205-207 ⁰ 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 420g (3 mol) of dihydroisophorone (3,3,5-trimethyl-cyclohexan-i on) presented at 28-30 ° C. Dry HCl gas was introduced into this solution at 28-3O ⁰ C for 5 hours. It is allowed to react for about 10 h at 28-30 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 80 ⁰ C and then cooled to 25 ° C. The aqueous phase is decanted off and the remaining residue washed with water at 8O ⁰ C. The crude product obtained is filtered off and extracted twice in each case with η-hexane and meth / dichlorene and filtered. The residue 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 stirred 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-cycluhexan-i-on ) submitted to 3O ⁰ C. 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%

Turnover of the ketone (GC control) is added to the reaction mixture 21 and water by addition of 45% NaOH solution has a pH of 6 a. The reaction mixture is stirred for one hour at 80 ° C and then cooled to 25 ° C. The aqueous phase is decanted off and the remaining residue is washed with water at 80.degree. The crude product obtained is filtered off and extracted in each case twice with η-hexane and toluene hot and filtered at 3O ⁰ C.

Yield: 253g Melting point: 205-208 ⁰ C.

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 is added g phenol in about 560ml of methylene chloride., 13 to 14 and 21 to 25 ⁰ C 19,8g (0.2 mol) of phosgene at a pH in the well-stirred solution. Then, 0.1 ml of ethyl pyridine is added and stirring continued for 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 made ready for use by the solvent The polycarbonate had a relative solution viscosity of 1.259.

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

Example B.2

68.4 g (0.3 mol) of bisphenol A (2,2-bis (4-hydroxyphenyl) propane, 217.0 g (0.7 mol) of diphenol according to Example (A.1), 336.6 g (6 mol KOH and 2700g water are dissolved in an inert gas Atmosphära with stirring. Then is added to a solution of 1.88 g of phenol in 2,500 ml of methylene chloride. into the well stirred solution at pH 13 to 14 and 21 to 25 ⁰ C 198g (2 moles Thereafter, 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 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 1.386.

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

Example B.4

As in Example B.2, a mixture of 159.6 g (0.7 mol) of bisphenol A and 93 g (0.3 mol) of diphenol was reacted according to Example (A.3) to 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.7

3,875 kg (12.5 moles) of bisphenol according to Example (A.2) are dissolved in 6.675 kg of 45% strength NaOH and 301 parts 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, dip organic phase acidified with phosphoric acid and then washed free of electrolyte and freed from the solvent.

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. 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. 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

Example D (film production)

20 g of the polycarbonates from Example B.1 were dissolved in 200 ml of methylene chloride with constant stirring at 3O ⁰ C, the solution thickened and then prepared by pouring onto a flat glass plate at 25 ⁰ C, a film of a thickness of 204 μιη.

This film was dried at 9O ⁰ C under vacuum for 4 hours, then the gas permeability was measured by this film.

Determination of gas permeability 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:

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

The measuring arrangement consists of a thermostated Zwai chamber system. The 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 gas) then causes in the permeate chamber at a constant volume, a pressure increase, which is registered with a pressure transducer (Baratron the Fa. MKS) as a function of time to the stationary gas passage. From the increase in pressure V (for normal pressure and normal temperature) can be calculated, t is bekamt. Δρ is set to 10 ⁵ Pa, taking into account the external air pressure. The membrane area F is known. Diameter thickness d is determined by means of a micrometer screw as a mean of 10 independent thickness measurements distributed over the membrane surface.

For these reasons, in the permeation coefficient P according to (1) to be determined in the dimension

öm3 (NTP) · mm m ² . 24h 10 ⁵ Pa

being based on a membrane thickness of 1 mm

 Further measuring parameters are:

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

Result: Permeation coefficients

for O ₂ : 280.8

for N ₂ : 84.5

KkCO ₂ : 2174.0

for CH ₄ : 149.4

The film was still dimensionally stable at 18O ⁰ C.

D.2 (comparative example)

According to Example D.1, a film of bisphenol A polycarbonate with a relative viscosity of 1.28 was prepared (thickness: 154 pm) and measured.

Result: Pormeation coefficient

for O ₂ : 7? 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, a film of thickness 92 pm is produced from 20 g of the polycarbonate from Example B.12 and the gas permeability is then measured.

Example D.4

As described in Example D.1, from 20 g of Po'ycarbonates from Example B.13 made a film of thickness 95pm and then measured the gas permeability.

Example D.5

As described in Example D.1, a film of thickness 89.7 μm is produced from 20 g of the polycarbonate from Example B.14, and the gas permeability is then measured.

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 with a thickness of 163 pm 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. In the well-stirred solution at pH 13-14 and 20-25 ⁰ C initiated 19,8g phosgene. 5 minutes after completion of Einkitons 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. From the concentrated solution in methylene chloride was poured a film which was clearly transparent. GPC analysis: Molecular weight was determined based on calibration with bisphenol A polycarbonate.

M _w = 246000, M _n = 38760 Results Permeation Values:

N ₂ Permeationsgase O ₂ 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

n. b .: not determined

D.8 (composite foil)

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 atwa 234 bar for 4 minutes to form a film having a thickness of about 307 μιη.

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

Result: permeation coefficient

for O ₂ : 208.3 for CO ₂ : 1 209.4 for CH ₄ : 77.1

This composite film was also at 18O ⁰ C dimensionally stable.

Example D.9

Composite film of polycarbonate according to Example B.14 and polymethyl methacrylate A polymethyl methacrylate (PMMA) film having a thickness of 130 μm and a film of polycarbonate B.14 having a thickness of 131 μm are pre-heated at 160 ° C. under a pressure of 200 bar pressed. 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 (Polystyrol N 168 from BASF AG) with a thickness of 78 μm and a film of polycarbonate B.14 with a thickness of 101 μm are stored at 16O ⁰ C after 30 seconds preheating Pressed a compacting pressure of 200 bar for 30 seconds to a composite film of thickness 168 pm. The gas permeabilities of the composite film were measured as described in Example D.1.

Results permeation values:

Permeation gases 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 pressure increase after gas presetting in a measuring cell was shown, the permeation value from the permeate after 3 days permeation time was determined.

Claims (1)

Claim: A composite film of a polycarbonate film and a film of another plastic, characterized in that the polycarbonate film consists of a high molecular weight, thermoplastic, aromatic polycarbonate having Mw (weight-average molecular weights) of at least 10,000, the bifunctional carbon structural units of the formula (Ia) (La)