NO174893B - High molecular weight, thermoplastic, aromatic polycarbonates, films thereof and use of the films - Google Patents

Description

The present invention relates to high-molecular, thermoplastic, aromatic polycarbonates. with fflw (weight average molecular weight) of at least 10,000, characterized in that they contain difunctional carbonate structural units of formula

(Ia)

in which

R<1> and R<2> independently of each other mean hydrogen, halogen,

C 1 -C 8 -alkyl, C 5 -C 6 -cycloalkyl, C 6 -C 10 -aryl and C 1 -C 4 -aralkyl,

m means an integer from 4 to 7,

R<3> and R^ are for each X individually selectable independently of

each other hydrogen or C 1 -C 4 -alkyl and

X means carbon atom,

provided that at least one X atom R<3> and R^ simultaneously mean alkyl,

in amounts of 100 mol-# to 2 mol-%, with regard to the total amount of 100 mol-% difunctional carbonate structural units in the polycarbonate and possibly also containing to 100 mol-% complementary amounts of difunctional structural units with formula

Foils of the above-mentioned polycarbonates as well as their use as a membrane for gas permeation are also described.

The diphenols with formula (I) give high-molecular, thermoplastic polycarbonates which are distinguished by high heat deformation resistance in combination with an otherwise good range of properties and are the subject of Norwegian patent application no. 893080.

A diphenol of formula (I) forming homopolycarbonates and also several diphenols of formula (I) forming copolycarbonates can also be used.

The high molecular weight polycarbonates from the diphenols of formula (I)

where R<1>, R<2>, R<3>, R<4>, X and m have the same meaning as for formula (Ia) according to the invention, possibly in combination with other diphenols can be prepared according to a known method of preparation of polycarbonates. Thereby, the different diphenols can be linked together both statistically and also as a block.

The object of the present invention is thus also a method for the production of high molecular weight thermoplastic, aromatic polycarbonates from diphenols, optionally chain terminating agents and optionally branching agents according to known methods for polycarbonate production, preferably through two-phase interface polycondensation, which is characterized by the use as diphenols of the formula ( I) in amounts of 100 mol% to 2 mol%, preferably in amounts of 100 mol% to 5 mol% and especially in amounts of 100 mol% to 10 mol%, particularly preferred is 100 mol% to 20 mol%, with regard to the total molar amount of added diphenols.

As a branching agent, if it is used, smaller amounts, preferably amounts between 0.05 and 2.0 mol-% (with regard to added diphenols) serve as branching agents, three or more often trifunctional compounds, especially those with three or more often such as triphenolic hydroxyl groups. Some of the useful compounds with three or most often triphenolic hydroxyl groups constitute

phloroglucin,

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-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, hexa-(4-(4 -hydroxyphenyl-isopropyl)-phenyl)-ortho-terephthalic acid ester,

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.

Monofunctional compounds in normal concentrations serve in a known manner as chain-breaking agents for regulating the molecular weight. Suitable compounds are e.g. phenol, tert-butyl phenols or other alkyl-C 1 -C 7 -substituted phenols. For regulating the molecular weights, particularly small amounts of phenols of formula (VIII) are suitable in which R provides a branched C8 and/or C8 alkyl residue. It is preferred that in the alkyl residue R the proportion of protons in the CH3 group is 47 to 89% and the proportion of protons in the CH and CE2 groups is 53 to 11%; it is also preferred that R is in the o- and/or p-position to the OH group, and the particularly preferred upper limit of the ortho part is 20$. The chain terminating agent is added in amounts of 0.5 to 10, preferably 1.5 to 8 mol-# with respect to diphenol.

The polycarbonates according to the invention can preferably be produced by phase interface polycondensation (cf. H. Schnell, "Chemistry and Physics of Polycarbonates", Polymer Reviews, Vol. IX, page 33 ff., Interscience Publ., 1964) in a manner known per se . In this way, the diphenols of formula (I) are dissolved in the aqueous alkaline phase. For the production of co-polycarbonates with other diphenols, mixtures of diphenols with formula (I) and the other diphenols, for example those with formula (VII) H0-Z-OH, are added. Suitable other diphenols of formula H0-Z-0H (VII) are those where Z is an aromatic residue with 6 to 30 C atoms which may contain one or more aromatic nuclei, be substituted and contain aliphatic residues or cycloaliphatic residues other than those with formula (I) or heteroatoms as bridging links. To regulate the molecular weight, chain-breaking agents can e.g. with formula (VIII) be added. Then, in the presence of an inert, preferably polycarbonate-dissolving, organic phase, they are reacted with phosgene according to the phase interface condensation method. The reaction temperature is between 0°C and 40°C.

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

Apart from the diphenols of formula (I) and the other diphenols (VII), other mono- and/or bischlorocarbonic acid esters can also be used as these are added dissolved in organic solvents. Amounts of chain-breaking agents and branching agents are directed at moles of diphenolate structural units of (I) and possibly of other di-phenols such as e.g. of (VII); likewise, by adding chlorocarbonic acid esters, amounts of phosgene can be correspondingly reduced in a known manner.

Suitable organic solvents for dissolving the chain terminating agent and possibly the branching agent and chlorocarbonic acid esters are e.g. methylene chloride, chlorobenzene, acetone, acetonitrile and mixtures of these solvents, especially mixtures of methylene chloride and chlorobenzene. Optionally, the chain terminating agents and branching agents used can be dissolved in similar solvents.

For example, methylene chloride, chlorobenzene and mixtures of methylene chloride and chlorobenzene serve as organic phase for phase interface polycondensation.

As an aqueous alkaline phase, e.g. aqueous NaOH solutions.

Formation of the polycarbonates according to the invention by phase interface polycondensation can normally be accelerated by means of catalysts such as tertiary amines, especially tertiary aliphatic amines such as tributylamine or triethylamine; the catalysts can be added in amounts of 0.05 to 10 mol-# with respect to the moles of added diphenols. The catalysts can be added before the start of the phosgenation or during or after the phosgenation.

Polycarbonates according to the invention can be separated in a known manner.

The high-molecular, thermoplastic aromatic polycarbonates according to the invention can also be produced according to a known method in a homogeneous phase, the so-called "pyridine method" as well as according to the known melt esterification method using e.g. diphenyl carbonate instead of phosgene. Here, too, the polycarbonates according to the invention can be insulated according to known techniques.

The polycarbonates obtained by the method according to the invention have preferred molecular weights Mw (weight average, obtained by gel chromatography after prior adjustment) of at least 10,000 g/mol, particularly preferably of 10,000 to 300,000 g/mol. If 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. If the polycarbonates according to the invention are used as molding foils, particularly preferred molecular weights Mw comprise between 100,000 and 250,000 g/mol. Polycarbonates according to the invention with Mw between 25,000 and 150,000 g/mol are preferred for the production of extrusion films. The polycarbonates according to the invention can be linear or branched, they are homopolycarbonates or copolycarbonates based on the diphenols of formula (I).

The object of the present invention is thus also high molecular weight thermoplastic, aromatic polycarbonates with Mw (weight average molecular weight) of at least 10,000, preferably of 10,000 to 300,000 and, for use in the injection molding area, especially of 20,000 to 80,000, which can be provided according to the method according to the invention from diphenols of formula (I), which are linear or branched.

The object of the present invention is thus also high-molecular, thermoplastic, aromatic polycarbonates with a Mw (weight average molecular weight) of at least 10,000, preferably of 10,000 to 300,000 g/mol and, for use in the injection molding area, especially of 20,000 to 80,000, which contain the bifunctional carbonate structural units with formula (Ia)

in which

X, R<1>, R<2>, R<3>, R<4> and m mean the same as stated in formula (Ia), p. 1,

in amounts of 100 mol-# to 2 mol-%, preferably in amounts of 100 mol-# to 5 mol-# and especially in amounts of 100 mol-% to 10 mol-# and particularly preferably 100 mol-% to 20 mol -# with regard to the total amount of 100 mol-% difunctional carbonate structural units in the polycarbonate.

The polycarbonates according to the invention thus contain complementary amounts of other difunctional carbonate structural units to 100 mol-#, e.g. with formula

(rest)

i.e. b.o.m. 0 mol-% up to and including 98 mol-%, preferably 0 mol-% to 95 mol-# and especially 0 mol-% to 90 mol-# and most preferred is 0 mol-# to 80 mol-% with regard to the total amount (of 100 mol- %) difunctional carbonate structural units in the polycarbonate.

Polycarbonate based on cycloaliphatic biphenols are mainly known and e.g. described in EP-A 164 476, DE-OS 33 45 945, DE-OS 20 63 052, FR-PS 14 27 998, WO 80 00 348, BE-PS 785 189. They often have relatively high freezing temperatures, but other important physical properties such as UV and heat aging stability are insufficient.

It has now surprisingly been shown that by incorporating the diphenols according to the invention with formula (I) new polycarbonates with a high thermal deformation resistance are provided which also otherwise exhibit other good properties. This applies especially to polycarbonates based on the diphenols (I) in which "m" means 4 or 5, and especially in those polycarbonates based on the diphenols (Ib)

in which

R<1> and R<2> independently of each other mean the same as stated in

formula (Ia) and preferably means hydrogen.

Thus, polycarbonates are preferably the subject of the invention in which the structural units of formula (Ia) m = 4 or 5 and preferably those with structural units of formula (Ic)

in which

R<1> and R<2> mean the same as stated in formula (Ia), but are preferably hydrogen.

These polycarbonates based on diphenols of formula (Ib), in which R<1> and R<2> in particular mean hydrogen, in addition to high heat resistance also have good UV stability and good flow conditions in the melt, and this was not expected.

Due to the free combinability with other diphenols, especially those with formula (VII), it is thus possible to vary the polycarbonate properties in a favorable way.

Isolation of the polycarbonates takes place in a known manner, whereby the organic phase obtained by the phase interface method is separated, neutrally and electrolyte-free washed and then, for example, isolated as granules over an evaporation extruder.

To the polycarbonate of the invention itself, the necessary quantities of the additives required for thermoplastic polycarbonate such as stabilizers, shaping agents, pigments, flame retardants, antistatic agents, fillers and reinforcing substances can be added either before or after processing.

Individually, e.g. carbon black, graphite, diatomaceous earth, kaolin, tone, CaF2, CaC03, aluminum oxide, glass fibres, barium sulphate and inorganic pigments are added both as fillers and as nucleating agents, as well as shaping agents e.g. glycerin stearate, pentaerythritol tetrastearate and trimethylolpropane tristearate.

The polycarbonates according to the invention can be processed into shaped bodies by, for example, extruding the polycarbonates isolated in a known manner into granules and processing these granules, if necessary, by adding the above-mentioned additives through injection molding into various articles.

The polycarbonates according to the invention can be added as moldings wherever they had previously been added, i.e. within the electrical sector as well as within the construction sector for uncovering and glazing, and even where increased heat mold resistance is required with simultaneous workability, i.e. when it is necessary to complicated building parts with high heat forming resistance.

Further uses of the polycarbonates according to the invention:

A.

As optical data storage devices, e.g. contact discs: Production of such data storage devices is known (see for example J. Hennig, Vortrag auf der Tagung "Neue Polymere" Bad Nauheim 14/15.04.1986 "Polymere als Substrate fiir optische Plattenspeicher" or Philips techn. Rev. 33, 178-180, 1973, No. 7 and 33, 186-189, 1973 Noi 7).

B.

For the production of safety routes.

Safety panes have a thickness of at least 2 mm to 10 mm and can be vaporized with SiOx where x has a value of 1 to 2 or be inserted in connection with glass panes. As is well known, safety routes are used in many areas such as buildings, vehicles and aircraft as well as protection and helmets.

C.

As lacquer raw materials.

D.

For the production of inflatable bodies (see e.g. US patent 2 964 794).

E.

For the production of light-transmitting plates, especially perforated chamber plates, e.g. for coating buildings such as railways, greenhouses and lighting systems.

F.

For the production of foams. (see e.g. DE-AS 1 031 507).

G.

For the production of cords and threads. (See e.g. DE-AS 1 137 167 and DE-OS 1 785 137).

H.

As translucent plastics with a glass fiber content for lighting purposes. (See e.g. DE-OS 1 544 020).

IN.

For the production of precision injection molded parts such as e.g. lens holders. For this, polycarbonates are used which have a glass fiber content of possibly approximately 1% by weight to 10% by weight of M0S2 with respect to the total weight.

K.

For the manufacture of optical device parts, in particular lenses for photo and film cameras. (See e.g. DE-OS 2 701 173).

L.

As light transmission conductors, especially optical fiber cables. (See e.g. EP-OS 0 089 801).

M.

As electroinsulating materials for electrical conductors.

0.

As carrier materials for organic photoconductors.

p.

For the manufacture of lanterns, e.g. floodlights, as well as so-called "head-stretching lamps" or.straight lines.

Foils can be produced from the high-molecular aromatic polycarbonates according to the invention. The foils have a preferred thickness of between 1 and 1500 ytm, particularly preferred is a thickness of between 10 and 900 pm.

The foils obtained can be stretched monoaxially or biaxially in a manner known per se, preferably in a ratio of 1:1.5 to 1:3.

According to a known method, the foils can be made into foils, e.g. by extrusion of a polymer melt through a wide slot die through blowing on a foil blowing machine, deep drawing or casting. In this way, a concentrated solution of the polymer in a suitable solvent is poured onto a flat surface, the solvent evaporates and the formed foil is lifted from the surface.

The foils can be stretched in a manner known per se to known devices at temperatures of between room temperature and a temperature where the viscosity of the polymer melt is not too much reduced, generally to approximately 370°C.

The foil production by casting the polycarbonate solutions takes place, for example, by casting concentrated solutions of the polycarbonate in a suitable solvent on smooth surfaces and finally evaporating the solvent by temperature control of the smooth surface between room temperature and 150°C. One can also apply the concentrated solutions of the polycarbonates to liquids, which have a higher density than the concentrated solutions, which are not compatible with the solvents used and which do not dissolve the polycarbonate, and after spraying the foil by evaporation recover the solvent used for the polycarbonate and possibly also the liquid with higher density.

The foils according to the invention have a particularly high thermal deformation resistance and are liquid for many gases. They can also be used as membranes for gas permeation.

It is also possible to use these foils alone.

Composite foils can also be produced with other plastic foils, since in principle, depending on the desired application and final properties of the composite foil, all known foils can be used as partners. For example, a composite of two or more foils can be provided by placing the single foil, under the polycarbonate foil according to the invention, on top of each other and at suitable temperatures which depend on the weak point of the individual foils, pressed together using pressure. You can also use the known foil co-extrusion method.

Production of the composite foils takes place in such a way that the foils for the individual components are first produced in a known, respectively above-described manner at optimal temperature control. Finally, the uncooled foils are brought to the same temperature without much stretching, which is preferably between room temperature and 370°C. The foils are then brought together over rollers and pressed together for a short time. For this, a pressure of between 2 and 500 bar is used. The procedure can also be carried out with more than one foil other than that of the polycarbonate, as the other foils are first brought together in the previously known manner and then pressed together with the foil of the polycarbonates under the above-mentioned pressure.

The foils or composite foils can be produced in a known manner and used as homogeneous membranes, composition membranes or asymmetric membranes. The membranes, foils or composite foils can be flat, form hollow bodies with different geometries, cylindrical, spherical, snake-shaped, or also as hollow fibres. Such shaped parts can be produced by the person skilled in the art according to known methods.

As polymers that can be used for the production of composite foils with the polycarbonate foils according to the invention, everything applies depending on what they are to be used for different polymers which will be listed below. Depending on the application, one can thus also provide composite foils that are not gas-permeable, which according to the state of the art have a better heat-form resistance, or one can obtain heat-form-resistant, gas-permeable composite foils, depending on the choice of composite partner.

Listed below are materials that provide foils that can be combined with the foil according to the invention.

As component (b), suitable thermoplastics are

bl) amorphous thermoplastics, preferably those with a glass transition temperature of more than 40°C, especially of 60°C to 220°C, and

b2) semi-crystalline thermoplastics, preferably those with a melting temperature of more than 60°C, especially of 80°C to 400°C.

Elastomers for components b) are

b3) those with a glass temperature of below 0°C, preferably below -10°C and especially from -15°C to -140°C.

The thermoplastic polycarbonates can be used both individually and also in a mixture as component b).

Preferred thermoplastics also comprise aliphatic, thermoplastic polyesters, particularly preferred is polyalkylene terphthalate, e.g. on the basis of ethylene glycol, propanediol-1,3, butanediol-1,4, hexanediol-1,6 and - 1,4-bis-hydroxymethyl-cyclohexane.

Further preferred other thermoplastics are thermoplastic polyamides.

Other preferred thermoplastics b) are also thermoplastic linear or branched polyarylene sulphides. They also have structural unity with general formula

wherein R 1 to R 4 may be the same or different and mean C 1 -C 6 alkyl, phenyl or hydrogen. The polyarylene sulfides can also contain diphenyl units.

Further preferred other thermoplastics b) are thermoplastic polyarylene sulfone.

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

Preferred other thermoplastics b) also constitute only aromatic polyether ketones (see e.g. GB-PS 1 078 234, US-PS 4 010 147 and EP-OS 0 135 938), apart from those based on diphenols of formula I.

They contain the repeating structural element

-0-E-O-E'- ,

wherein -E'- means the bivalent residue of a bisaryl ketone and

-0-E-O- the bivalent diphenolate residue.

Other preferred thermoplastics b) are also thermoplastic vinyl polymers.

The thermoplastic poly-C 1 -C 4 -alkyl methacrylates suitable according to the invention are known in the literature or can be obtained according to known methods.

Other preferred thermoplastics b) are also thermoplastic polyurethane. These constitute reaction products of diisocyanates, wholly or predominantly aliphatic oligo- and/or polyesters and/or ethers as well as one or more chain extenders. These thermoplastic polyurethanes are substantially linear and have thermoplastic processing characteristics.

Other preferred thermoplastics also comprise aromatic polyester carbonates.

Thermoplastic b) insertable aromatic polyesters and polyester carbonates are made up of at least one aromatic bisphenol, e.g. with formula (VII), and at least one aromatic dicarboxylic acid and optionally of carboxylic acid.

The foils, respectively the composite foils, can be flat, hollow, spherical, snake-shaped and hollow fiber-shaped. According to known methods, these foils can be provided by re-forming, deep drawing, blowing, etc.

The foils according to the invention, especially the composite foils, are used, for example, in cooking and oven-proof packaging and in microwave-proof packaging, depending on which components b) the composite foils according to the invention are made up of.

The composite foils according to the invention can be provided by coextrusion of the thermoplastic plastic with the polycarbonates according to the invention in a working procedure.

A

The foils produced from the polycarbonates according to the invention and the composite foils according to the invention based on these foils from the polycarbonates according to the invention can be used as homogeneous membranes, composition membranes or asymmetric membranes.

In the examples below, the relative viscosity is measured in 0.5 wt% solution of the polycarbonates in CH2C12-

The freezing temperature or glass transition temperature is measured by differential scanning calorimetry (DSC).

Example A. l

Preparation of diphenols of formula (II)

Into a 1 L round bottom flask with stirrer, dropping funnel, thermometer, reflux condenser and gas inlet tube 7.5 mol (705 g) phenol and 0.15 mol (30.3 g) dodecylthiol are added and at 28 to 30°C saturated with dry HCl -gas. To this solution, a solution of 1.5 mol (210 g) of dihydroisophorone (3,3,5-trimethyl-cyclohexan-1-one) and 1.5 mol (151 g) of phenol is added dropwise over the course of 3 hours, further HCl gas is introduced into the reaction solution. After the end of dropwise addition, HCl gas is fed in for a further 5 hours. This is left to react for 8 hours at room temperature. Finally, excess phenol is removed by steam distillation. The remaining residue is hot-extracted twice with petroleum ether (60-90) and once with methylene chloride and then filtered off.

Yield: 370 g

Melting point: 205 to 207°C

Example A. 2

Preparation of diphenols of formula (II)

In a tube apparatus with stirrer, thermometer, reflux condenser and gas inlet tube, 1692 g (18 mol) phenol, 606 g (0.3 mol) dodecylthiol and 420 g (3 mol) dihydroisophorone (3,3,5-trimethyl-cyclohexane-l- on) added at 28-30°C. Dried HCl gas is introduced into this solution at 28-30°C over the course of 5 hours. This reacts further for approx. 10 hours at 28-30°C. After 95% conversion of the ketones (GC control) 2.5 1 of water is added to the reaction mixture and a pH value of 6 is set by adding the 45% NaOH solution. 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° C. The crude product obtained is filtered off and hot-extracted. times with n-hexane and methylene chloride and filtered. The remainder is recrystallized-1 in cert twice from xylene.

Yield: 753 g

Melting point: 209-211°C

Example A. 3

Preparation of diphenols of formula (II)

564 g (6 mol) phenol, 10.8 g (0.12 mol) butanethiol and 140 g (1 mol) dihydroisophorone (3,3,5-trimethyl-cyclohexane -l-one) at 30°C. At this temperature, 44 g of 37$ HC1 are added. The reaction mixture is stirred at 28-30°C for approx. 70 hours. After 95% conversion of the ketones (GC control), 2 1 water is added to the reaction mixture and the pH value is adjusted to 6 with 45% NaOH solution. 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°C. The crude product obtained is filtered out and then hot-extracted twice with n-hexane and toluene and filtered out at 30°C.

Yield: 253 g

Melting point: 205-208°C

Example A. 4

Preparation of diphenols of formula (Ib), (R<1>, R<2> = CE3)

In a tube apparatus with stirrer, thermometer, reflux condenser and gas inlet tube, 2196 g (18 mol) of 2,6-dimethylphenol, 38.2 g (0.36 mol) of e-mercaptopropionic acid and 420 g (3 mol) of dihydroisophorone (3,3, 5-trimethyl-cyclohexan-1-one) added at 35°C. Dry HCl gas is introduced into this solution at 35°C for 5 hours. This is allowed to react for approx. 10 hours at 30-35°C. After 95% conversion of the ketones (GC control), 2.5 1 of water is added to the reaction mixture and a pH value of 6 is set by adding 45% NaOH solution. The reaction mixture is stirred for one hour at 80° C and then cooled to room temperature. The aqueous phase is decanted off and the remaining residue is washed with water at 60° C. The crude product obtained is filtered off and hot-extracted three times with n-hexane and filtered.

Yield: 856 g

Melting point: 236-238°C

Example A. 5

Preparation of diphenols of formula (III)

Analogous to example A2, 3 mol of 3,3-dimethylcyclohexanone are added instead of 3 mol of dihydroisophorone. The product showed a melting point of 199-201°C.

The diphenols of formula (I) according to the invention give high-molecular, thermoplastic polycarbonates which are distinguished by high heat deformation resistance in combination with an otherwise good range of properties.

Example B. l

31.0 g (0.1 mol) diphenols (Example A.l), 33.6 g (0.6 mol) KOH and 560 g water are charged in an inert gas atmosphere with stirring. A solution of 0.188 g of phenol in 560 ml of methylene chloride is then added. Into the well-stirred solution was introduced 19.8 g (0.2 mol) of phosgene at pH 13 to 14 and at 21 to 25°C. Then 0.1 ml of ethylpyridine is added and it was stirred for a further 45 minutes. The bisphenolate-free aqueous phase is removed and the organic phase, after acidification with phosphoric acid, is washed to neutrality with water and the solvent is removed. The polycarbonate shows a relative solution viscosity of 1.259.

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

Example B. 2

68.4 g (0.3 mol) bisphenol A (2,2-bis-(4-hydroxyphenyl)-propane, 217.0 g (0.7 mol) diphenol (Example A.l), 336.6 g (6 mol KOH and 2,700 g of water were dissolved in an inert gas atmosphere with stirring. Then a solution of 1.88 g of phenol in 2,500 ml of methylene chloride was added. Into the well-stirred solution was introduced 198 g (2 mol) of phosgene at pH 13 to 14 and 21 to 25° C. Then 1 ml of ethyl piperidine is added and it was stirred for a further 45 min. The bisphenol-free aqueous phase is removed and the organic phase, after acidification with phosphoric acid, was washed to neutrality with water and separated from the solvent. The polycarbonate exhibits a relative solution viscosity of 1.336.

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

Example B. 3

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

The polycarbonate exhibits 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) bisphenol A and 93 g (0.3 mol) diphenol was converted into polycarbonate (example A.3).

The polycarbonate exhibited a relative solution viscosity' of 1.437.

The glass transition temperature of the polymers was determined to be 180°C (DSC).

Example B. 5

31.0 g (0.1 mol) of diphenol (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. A solution of 0.309 g of 4-(1,1,3,3-tetramethylbutyl)-phenol in 250 ml of methylene chloride is then added. Into the well-stirred solution was introduced 19.8 g (0.2 mol) of phosgene at pH 13 to 14 and 21 to 25<0>C. Then 0.1 ml of ethyl piperidine was added and it was stirred for a further 45 min. The bisphenolate-free aqueous phase is separated and the organic phase, after acidification with phosphoric acid, is washed neutrally with water and the solvent is removed. The polycarbonate exhibits a relative solution viscosity of 1.314.

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

To assess the UV resistance of the new polycarbonates, the primary radical formation by UV irradiation with a mercury vapor lamp (Kantenfilter 305 nm) was compared with a polycarbonate based on 2,2-bis-(4-hydroxyphenyl)-propane. It turned out that the polycarbonate according to example B.l exhibits a lower primary radical formation rate and thus a higher UV resistance.

Example B. 6

148.2 g (0.65 mol) 2,2-bis-(4-hydroxyphenyl)-propane, 108.5 g (0.35 mol) diphenol (Example A.l), 336.6 g (6 mol) KOH and 2,700 g of water are dissolved in an inert gas atmosphere with stirring. A solution of 8.86 g of 4-(1,1,3,3-tetramethylbutyl-phenol in 2,500 ml of methylene chloride is then added. In the well-stirred solution, 198 g (2 mol) of phosgene was added at pH 13 - 14 and 21 - 25° C. Then 1 ml of ethyl piperidine was added and stirred for a further 45 min. The bisphenolate-free aqueous phase is separated and the organic phase, after acidification with phosphoric acid, was washed neutral with water and solvents were removed. The polycarbonate exhibits a relative solution viscosity of 1, 20.

Example B. 7

3.875 kg (12.5 mol) of bisphenol (Example A.2) is dissolved in 6.675 kg of 45% NaOH and 30 L of water dissolved in an inert gas atmosphere with stirring. 9.43 1 of methylene chloride, 11.3 1 of chlorobenzene and 23.5 g of phenol are then added. Into the well-stirred solution, 2.475 kg of phosgene are introduced at pH 13 - 14 and 20-25°C. After the addition has ended, 12.5 ml of N-ethyl-piperidine is added. This is further reacted for 45 min. The bisphenolate-free aqueous phase is separated and the organic phase is acidified with phosphoric acid and finally washed electrolyte-free and the solvent is removed.

Rel. viscosity: 1,300

Glass transition temperature: 238°C

Example B. 8

15.5 g (0.05 mol) bisphenol (Example A.3), 13.4 g (0.05 mol) bis-(4-hydroxyphenyl)-cyclohexane (bisphenol Z), 24.0 g (0.6 mol ) of NaOH is dissolved in 362 ml of water in an inert gas atmosphere

while stirring. Then 0.516 g of 4-(1,1,3,3-tetramethyl-butyl)phenol dissolved in 271 ml of methylene chloride is added. In the well-stirred solution, 19.8 g of phosgene are added at pH 13 - 14 and 20-25°C. 5 min. After the addition is complete, 0.1 ml of N-ethylpiperidine is added. This is allowed to react for 45 minutes. The bisphenolate-free aqueous phase is separated and the organic phase is acidified with phosphoric acid and finally washed to neutrality and the solvent is removed.

Rel. viscosity: 1.297

Glass transition temperature: 208°C

Example B. 9

15.5 g (0.05 mol) of bisphenol (Example A.l), 17.6 g (0.05 mol) of 4,4'-dihydroxytetraphenylmethane, 24.0 g (0.6 mol) of NaOH are dissolved in 411 ml of water in an inert gas atmosphere with stirring. Next, 0.516 g of 4-(1,1,3,3-tetramethylbutyl)phenol is dissolved in 308 ml of methylene chloride and added. Into the well-stirred solution, 19.8 g of phosgene are introduced at pE 13-14 and 20-25°C. 5 minutes after the addition has ended, 0.1 ml of N-ethyl-piperidine is added. This is reacted for 45 min. The bisphenolate-free aqueous phase is separated and the organic phase acidified with phosphoric acid and finally washed to neutrality and separated from the solvent.

Rel. viscosity: 1.218

Glass transition temperature: 212°C

Example B. 10

18.3 g (0.05 mol) of bisphenol (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 is added. In the well-stirred solution, 17.3 g of phosgene are added at pE 13 - 14 and 20-25°C. 5 minutes after the addition has ended, 0.3 ml of N-ethylpiperidine is added. This is allowed to react for 45 minutes. The bisphenolate-free aqueous phase is separated and the organic phase is acidified with phosphoric acid and finally washed to neutrality and separated from the solvent.

Rel. viscosity: 1.310

Glass transition temperature: 241°C

Example B. ll

29.6 g (0.1 mol) of bisphenol (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. Next, 0.413 g of 4-(1,1,3,3-tetramethyl-butyl)phenol is dissolved in 277 ml of methylene chloride and added. In the well-stirred solution, 19.8 g of phosgene are added at pH 13 - 14 and 20-25°C. 5 minutes after the addition has ended, 0.1 ml of N-ethylpiperidine is added. This is allowed to react for 45 minutes. The bisphenolate-free aqueous phase is then separated and the organic phase is acidified with phosphoric acid and then washed to neutrality and the solvent is removed.

Rel. viscosity: 1.370

Glass transition temperature: 193"C

Example B. 12

62.0 g (0.2 mol) bisphenol (Example A.l), 182.4 g (0.8 mol) bisphenol A, 240 g (6 mol) NaOH are dissolved in 2,400 ml of water in an inert gas atmosphere with stirring . Next, 6.603 g of 4-(1,1,3,3-tetramethylbutyl)phenol is dissolved in 2,400 ml of methylene chloride and added. In the well-stirred solution, 198 g of phosgene are added at pH 13 - 14 and 20-25oC. 5 minutes after the addition has ended, 1 ml of N-ethyl-piperidine is added. This is allowed to react for 45 minutes. The bisphenolate-free aqueous phase is separated and the organic phase is acidified with phosphoric acid and finally washed to neutrality and the solvent is removed.

Rel. viscosity: 1.298

Glass transition temperature: 172"C

Example B. 13

170.5 g (0.55 mol) bisphenol (example A.3), 102.6 g (0.45 mol) bisphenol A, 240 g (6 mol) NaOH are dissolved in 2,400 ml of water in an inert gas atmosphere while stirring. Next, 5.158 g of 4-(1,1,3,3-tetramethylbutyl)phenol is dissolved in 2,400 ml of methylene chloride and added. In the well-stirred solution

198 g of phosgene are added at pH 13 - 14 and 20-25°C. 5 minutes after the addition has ended, 1 ml of N-ethylpiperidine is added. This is allowed to react for 45 minutes. The bisphenolate-free aqueous phase is separated and the organic phase is acidified with phosphoric acid and finally washed to a neutral state and the solvent is removed.

Rel. viscosity: 1.302

Glass transition temperature: 203'C

Example B. 14

108.5 g (0.35 mol) bisphenol (Example A.l), 148.2 g (0.65 mol) bisphenol A, 240 g (6 mol) NaOH are dissolved in 2,400 ml of water in an inert gas atmosphere with stirring . Next, 6.189 g of 4-(1,1,3,3-tetramethylbutyl)phenol is dissolved in 2,400 ml of methylene chloride and added. The well-stirred solution is added with 198 g of phosgene at pH 13 - 14 and 20-25° C. 5 minutes after the end of the addition, 1 ml of N-ethylpiperidine is added. This is allowed to react for 45 minutes. The bisphenolate-free aqueous phase is separated and the organic phase acidified with phosphoric acid and finally washed to neutrality and the solvent is removed.

Rel. viscosity: 1.305

Glass transition temperature: 185 °C

Example C

From copolycarbonate according to example B.6 and from a bisphenol-A homopolycarbonate with Hrel = 1>20, compact discs with a diameter of 12 cm were produced on a Netstal injection molding machine (mass temperature 330 to 350°C). The birefringence in the axial direction was checked by means of time difference measurement using ordinary comparators by means of a polarization microscope. The transparency was assessed visually and the glass transition temperature was determined by DSC.

Example D (production of foil)

D.l

20 g of the polycarbonates from example B.l were dissolved in 200 ml of methylene chloride with constant stirring at 30°C, the solution was boiled in and finally a foil with a thickness of 204 pm was produced by casting on a flat glass surface at 25°C. This foil was dried for 4 hours at 90° C. under vacuum, then the gas flow through the foil was measured.

Determination of the gas flow (permeation) in polymer membranes

The passage of a gas through a dense polymer membrane is determined through a solution-diffusion method. The characteristic constants for this process are the permeation coefficient P which indicates which gas volume V at a specified pressure difference Ap in a specific time t passes through a foil of known surface area F and thickness d. For stationary conditions, the permeation course can be derived from the differential equations:

The permeation depends on the temperature and the water content of the gases.

The measuring device consists of a thermostatic two-chamber system. One chamber is for the absorption of pre-addition gases and the other chamber is for the absorption of permeate. The chambers are separated by the polymer membrane that is measured.

Both chambers are evacuated at 10-<3> mbar and the preaddition chamber is then filled with gas. The permeable gas (inert gas) then provides in the permeate chamber at constant volume a pressure increase which is registered with a pressure recorder (Baratron der Fa. MKS) depending on the time until the stationary gas passage. From the pressure increase, V (for normal pressure and normal temperature) can be calculated, t is known. Taking into account the external air pressure, Ap is set to IO<5> Pa. Membrane surface F is known. Membrane thickness Isen d is determined using a micrometer screw as an average from 10 independent thickness measurements distributed over the membrane surface.

For these sizes, the permeation coefficient P is determined according to (1) in which the dimensions

is with regard to a membrane thickness of 1 mm.

Additional measurement parameters are:

Temperature: 25 ± 1'C

Rel. gas humidity: 0$

Results: Permeation coefficient

The foil was still pre-stable at 180°C.

D.2 (comparison example)

Corresponding to example D.1, a film of bisphenol-A polycarbonate with a relative viscosity of 1.28 was produced (thickness: 154 pm) and measured.

Results: Permeation coefficient

At 180°C, this foil was no longer dimensionally stable.

Example D. 3

As described in example D.1, a foil was produced from 20 g of polycarbonates from example B.12 with a thickness of 92 µm and then the gas permeability was measured.

Example D. 4

As described in example D.1, a foil was produced from 20 g of polycarbonates from example B.13 with a thickness of 95 µm and finally the gas flow was measured.

Example D. 5

As described in example D.1, a foil with a thickness of 89.7 µm was produced from 20 g of the polycarbonates in example B.14 and finally the gas permeability was measured.

Example D. 6

The polycarbonate from Example B.7 was melted in an extruder (temperature: 360-370°C) and extruded over wide-slit dies to a foil with a thickness of 163 µm and finally the gas permeability was measured.

Example D. 7

31 g (0.1 mol) of bisphenol A.l, 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 is added. In the well-stirred solution, 19.8 g of phosgene are added at pH 13 - 14 and 20-25°C. 5 minutes after the addition has ended, 0.1 ml of N-ethylpiperidine is added. This is left to react for a further 45 minutes. The bisphenolate-free aqueous phase is separated and the organic phase is acidified with phosphoric acid and finally washed to neutrality. A transparent film was cast on the concentrated solution in methylene chloride.

GPC analysis: The molecular weight was carried out on the basis of a calibration with bisphenol-A—polycarbonate.

Mw = 246,000, Mn = 38,760

Results permeation values:

i.b.: not determined

D.8 (composite foil)

The foils produced according to D.1 and D.2 were, after evaporation of the solvents, placed on top of each other and pressed together at 235°C and a pressure of approximately 234 bar for 4 minutes to a foil with a thickness of approximately 307 µm.

The gas permeability of the composite foil was measured as described in D.l.

Result: Permeation coefficient

These composite foils were also dimensionally stable at 180°C.

Example D. 9

Composite foils of polycarbonate according to example B.14 and polymethyl methacrylate

A polymethyl methacrylate foil (PMMA) with a thickness of 130 pm and a foil of polycarbonate B.14 with a thickness of 131 pm are pressed together at 160°C after 30 seconds of preheating under a pressure of 200 bar. The gas permeability in the composite foil was measured as described in example D.l.

Example D. 10

Composite foils of polycarbonate according to example B.14 and polystyrene

A polystyrene foil (polystyrene N 168 from BASF AG) with a thickness of 78 µm and a foil of polycarbonate B.14 with a thickness of 101 µm were pressed together at 160°C after 30 seconds of preheating under a pressing pressure of 200 bar for 30 seconds more a composite foil with a thickness of 168 pm. The gas permeability of the composite foil was measured as described in Example D.l.

Results permeation values:

Claims (10)

1. High-molecular, thermoplastic, aromatic polycarbonates with TOw (weight average molecular weight) of at least 10,000, characterized in that they contain difunctional carbonate structural units of formula (Ia) in which r! and R<2> independently of each other means hydrogen, halogen, C1-C8-alkyl, C5-C6-cycloalkyl, C6-C10-aryl and Cy-C-3-aralkyl" m means an integer from 4 to 7, R<3> and R<4> are for each X individually selectable independently of each other hydrogen or C₁-C₂-alkyl and X means a carbon atom, provided that at least one X atom R<3> and R<4> simultaneously mean alkyl, in amounts of 100 mol-% to 2 mol-%, with regard to the total amount of 100 mol-$ difunctional carbonate structural units in the polycarbonate and possibly also containing up to 100 mol-% complementary amounts of difunctional structure units with formula 2. Polycarbonates according to claim 1, characterized in that they contain the structural units of formula (Ia) in amounts of 100 mol-% to 5 mol-$. 3. Polycarbonates according to claim 1, characterized in that m in formula (Ia) is 4 or 5. 4. Polycarbonates according to claim 1, characterized in that they contain structural units of formula (Ic) in which R<1> and R<2> mean the same as for formula (Ia) in claim 1. 5 . Polycarbonates according to claim 1, characterized in that they contain structural units of formula (Ila) 6. Films, characterized in that they are made of polycarbonates according to claim 1. 7 . Foils, characterized in that they are made of polycarbonate according to claim 1 and with a thickness of 1-1,500 pm. 8. Foils, characterized in that they are made of polycarbonates according to claim 1, with a thickness of 1-1,500 pm, which are mono- or biaxially stretched in a ratio of 1:1.5 to 1:3.0. 9. Composite foils, characterized in that they are of a foil according to claim 1, and a foil of another synthetic material. 10. Use of the films according to claim 6, as a membrane for gas permeation.