DE3832396A1 - Dihydroxydiphenylcycloalkanes, their preparation, and their use for the preparation of high-molecular-weight polycarbonates - Google Patents

Abstract

The present invention relates to dihydroxydiphenylcycloalkanes of the formula (I) <IMAGE> in which R<1> and R<2> independently of one another represent hydrogen, halogen, C1-C8-alkyl, C5-C6-cycloalkyl, C6-C10-aryl and C7-C 12-aralkyl, m is an integer from 4 to 7, R<3> and R<4> can be selected individually for each X and, independently of one another, represent hydrogen or a C1-C6-alkyl and X represents carbon, with the proviso that X, R<3> and R<4> on at least one atom are simultaneously alkyl, to a process for their preparation, and to the use of the diphenols of the formula (I) for the preparation of high-molecular-weight polycarbonates.

Description

The present invention relates to dihydroxydiphenylcycloalkanes of formula (I)

wherein
R¹ and R² independently of one another are hydrogen, halogen, preferably chlorine or bromine, C₁-C₈-alkyl, C₅-C₆-cycloalkyl, C₆-C₁₀-aryl, preferably phenyl, and C₇-C₁₂-aralkyl, preferably phenyl-C₁-C₄-alkyl , especially benzyl,
m is an integer from 4 to 7, preferably 4 or 5,
R³ and R⁴, individually selectable for each X, independently of one another hydrogen or C₁-C₆-alkyl
and
X is carbon,
with the proviso that on at least one atom X R³ and R⁴ simultaneously mean alkyl.

Alkyl at 1-2 atoms, in particular only at one atom X, R³ and R⁴ are preferred at the same time. The preferred alkyl radical is methyl; the X atoms in the α position to the di-phenyl-substituted C atom (C-1) are preferably not dialkyl-substituted, whereas the alkyl disubstitution in the β position to C-1 is preferred. In particular, the invention relates to dihydroxydiphenylcycloalkanes having 5 and 6 ring carbon atoms in the cycloaliphatic radical (m = 4 or 5) in formula (I), such as, for example, the diphenols of the formulas

the 1,1-bis (4-hydroxyphenyl) -3.3.5.trimethylcyclohexane (Formula II) is particularly preferred.

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

and ketones of the formula (VI)

are prepared, wherein in formulas (V) and (VI) X, R¹, R², R³, R⁴ and m have the meaning given for formula (I).

The phenols of formula (V) are either known from the literature or available by methods known from the literature (see for example for cresols and xylenols, Ullmann's Encyclopedia of Chemical Engineering, 4. revised and expanded edition, volume 15, pages 61-77, Verlag Chemie-Weinheim-New York 1978; For Chlorphenols, Ullmann's encyclopedia of technical Chemistry, 4th edition, Verlag Chemie, 1975, volume 9, pages 573-582; and for alkylphenols, Ullmann's encyclopedia of technical chemistry, 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, diphenylphenol and o, - or p-benzylphenols.

The ketones of the formula (VI) are known from the literature (see for example) Beilstein's handbook of organic Chemistry, 7th volume, 4th edition, Springer-Verlag, Berlin, 1925, and the corresponding supplementary volumes 1 to 4, and J. Am. Chem. Soc. Vol 79 (1957), pages 1488, 1490 and 1491, U.S. Patent 2,692,289, Allen et al., J. Chem. Soc., (1954), 2186, 2191, and J. Org. Chem. Vol. 38, No. 26, (1973), pages 4431ff, J. Am. Chem. Soc. 87, (1965), Pages 1353ff, especially pages 1355. A general one Process for the preparation of ketones of formula (VI) is, for example, in "Organikum", 15th edition, 1977, VEB-German Publishing House of Sciences, Berlin, for example Page 698.  

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

3,3-dimethylcyclopentanone, 2,2-dimethylcyclohexanone, 3,3-dimethylcyclohexanone, 4,4-dimethylcyclohexanone, 3- Ethyl 3-methylcyclopentanone, 2,3,3-trimethylcyclopen tanon, 2,4,4-trimethylcyclopentanone, 3,3,4-trimethyl cyclopentanone, 3,3-dimethylcycloheptanone, 4,4-dimethyl cycloheptanone, 3-ethyl-3-methylcyclohexanone, 4-ethyl-4- methylcyclohexanone, 2,3,3-trimethylcyclohexanone, 2,4,4- Trimethylcyclohexanone, 3,3,4-trimethylcyclohexanone, 2,5,5-trimethylcyclohexanone, 3,3,5-trimethylcyclohexa non, 3,4,4-trimethylcyclohexanone, 2,3,3,4-tetramethyl cyclopentanone, 2,3,4,4-tetramethylcyclopentanone, 3,3,4,4-tetramethylcyclopentanone, 2,2,5-trimethylcyclo heptanone, 2,2,6-trimethylcycloheptanone, 2,6,6-trimethyl cycloheptanone, 3,3,5-trimethylcycloheptanone, 3,5,5- Trimethylcycloheptanone, 5-ethyl-2,5-dimethylcyclohep tanon, 2,3,3,5-tetramethylcycloheptanone, 2,3,5,5-tetra methylcycloheptanone, 3,3,5,5-tetramethylcycloheptanone, 4-ethyl-2,3,4-trimethylcyclopentanone, 2-isopropyl-4,4- dimethylcyclopentanone, 4-isopropyl-2,4-dimethylcyclo pentanone, 2-ethyl-3,5,5-trimethylcyclohexanone, 3-ethyl 3,5,5-trimethylcyclohexanone, 3-ethyl-4-isopropyl-3- methyl-cyclopentanone, 4-sec. Butyl-3,3-dimethylcyclo pentanone, 2-isopropyl-3,3,4-trimethylcyclopentanone, 3- Ethyl 4-isopropyl-3-methyl-cyclohexanone, 4-ethyl-3-iso propyl-4-methyl-cyclohexanone, 3-sec. Butyl-4,4-dimethyl cyclohexanone, 3-isopropyl-3,5,5-trimethylcyclohexanone, 4-isopropyl-3,5,5-trimethylcyclohexanone, 3,3,5-tri methyl-5-propylcyclohexanone, 3,5,5-trimethyl-5-propyl  cyclohexanone, 2-butyl-3,3,4-trimethylcyclopentanone, 2- Butyl-3,3,4-trimethylcyclohexanone, 4-butyl-3,3,5-tri methylcyclohexanone, 3-isohexyl-3-methylcyclohexanone, 5- Ethyl 2,4-diisopropyl-5-methylcyclohexanone, 2,2-di methylcyclooctanone and 3,3,8-trimethylcyclooctanone.

Examples of preferred ketones are

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

The condensation generally becomes more acidic in the presence Catalysts carried out. 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 can be carried out by adding cocatalysts such as C₁-C₁₈ alkyl mercaptans, hydrogen sulfide, Accelerated thiophenols, thioacids and dialkyl sulfides will.

The condensation can be without solvent or in the presence an inert solvent (e.g. aliphatic and aromatic hydrocarbon, chlorinated hydrocarbon) be performed.

In cases where the catalyst is used simultaneously as dehydrating agent acts, it is not necessary use additional dehydrating agents, the latter, however, is to achieve good sales in any case advantageous if the one used Catalyst that does not bind water of reaction.

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

The present invention is therefore also an object a process for the preparation of the dihydroxydiphenylcycloalkanes of formula (I)  

wherein
R¹ and R² independently of one another are hydrogen, halogen, preferably chlorine or bromine, C₁-C₈-alkyl, C₅-C₆-cycloalkyl, C₆-C₁₀-aryl, preferably phenyl, and C₇-C₁₂-aralkyl, preferably phenyl-C₁-C₄-alkyl , especially benzyl,
m are an integer from 4 to 7, preferably 4 or 5,
R³ and R⁴, individually selectable for each X, independently of one another hydrogen or C₁-C₆-alkyl
and
X is carbon
with the proviso that on at least one atom X R³ and R⁴ simultaneously mean alkyl,
which is characterized in that phenols of the formula (V)

wherein
R¹ and R² have the meaning given for formula (I),
with ketones of the formula (VI)

wherein
X, m , R³ and R⁴ have the meaning given for formula (I),
in the molar ratio (V): (VI) between 2: 1 and 10: 1, preferably between 2.5: 1 and 6: 1, at temperatures between -30 ° C and 300 ° C, preferably between -15 ° C and 150 ° C, and at pressures from 1 to 20 bar, preferably from 1 to 10 bar, in the presence of acidic catalysts and optionally in the presence of co-catalysts and / or solvents and / or dehydrating agents.

In formula (I) at 1-2 atoms X, in particular only on one atom X, R³ and R⁴, alkyl are preferred at the same time. The preferred alkyl radical is methyl; ethyl or C₃-C₆-alkyl radicals, which can be straight-chain or branched, can also be used. The X atoms in the a position to the di-phenyl-substituted C atom (C-1) are preferably not dialkyl-substituted, but disubstitution with alkyl in the β position in C-1 is preferred.

In some cases, the reaction is not entirely uniform, d. H. there can be several different products arise so that the desired connection first must be isolated from a mixture. For details condensation on Schnell, Chemistry and Physics of Polycarbonates, Interscience Publishers, New York 1964. Sometimes the reaction by choosing appropriate catalysts and Reaction conditions are controlled so that the desired compound fails or crystallizes out, which facilitates their isolation.  

Example A Preparation of diphenol (II)

In a 1 liter round bottom flask with stirrer, dropping funnel, Thermometer, reflux condenser and gas inlet pipe 7.5 mol (705 g) of phenol and 0.15 mol (30.3 g) Dodecylthiol submitted and at 28 to 30 ° C with dry HCl gas saturated. To this solution within 3 hours a solution of 1.5 moles (210 g) dihydroisophorone (3,3,5-trimethyl-cyclohexan-1-one) and 1.5 mol (151 g) phenol was added dropwise, with further HCl gas passing through the reaction solution is fed. After the addition is complete HCl gas is passed in for a further 5 hours. Man allows to react for 8 h at room temperature. Subsequently the excess phenol is removed by steam distillation away. The remaining residue will twice with petroleum ether (60-90) and once with methylene chloride extracted hot and filtered.

Yield: 370 g
Melting point: 205 to 207 ° C

The diphenols of formula (I) according to the invention are in particular suitable for the production of high molecular, thermoplastic polycarbonates, which are characterized by high Heat resistance in combination with a good one distinguish other characteristics.

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

Both a diphenol of formula (I) can be formed of homopolycarbonates as well as several diphenols of formula (I) used to form copolycarbonates will.

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

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

Examples of diphenols of the formula (VII) are
Hydroquinone,
Resorcinol,
Dihydroxydiphenyls,
Bis (hydroxyphenyl) alkanes,
Bis (hydroxyphenyl) cycloalkanes,
Bis (hydroxyphenyl) sulfides,
Bis (hydroxyphenyl) ether,
Bis (hydroxyphenyl) ketones,
Bis (hydroxyphenyl) sulfones,
Bis (hydroxyphenyl) sulfoxides,
α , α- bis (hydroxyphenyl) diisopropylbenzenes
and their nuclear alkylated and nuclear halogenated compounds.

These and other suitable other diphenols are e.g. B. in US-PS 30 28 365, 29 99 835, 31 48 172, 32 75 601, 29 91 273, 32 71 367, 30 62 781, 29 70 131 and 29 99 846, in German Offenlegungsschriften 15 70 703, 20 63 050, 20 63 052, 2 21 10 956, the French Patent 15 61 518 and in the monograph "H. Schnell, Chemistry and Physics of Polycarbonates, Interscience Publishers, New York 1964 ".

Preferred other diphenols are, for example:
4,4'-dihydroxydiphenyl,
2,2-bis (4-hydroxyphenyl) propane,
2,4-bis (4-hydroxyphenyl) -2-methylbutane,
1,1-bis (4-hydroxyphenyl) cyclohexane,
α , α ′ -Bis- (4-hydroxyphenyl) -p-diisopropylbenzene,
2,2-bis (3-methyl-4-hydroxyphenyl) propane,
2,2-bis (3-chloro-4-hydroxyphenyl) propane,
Bis (3,5-dimethyl-4-hydroxyphenyl) methane,
2,2-bis (3,5-dimethyl-4-hydroxyphenyl) propane,
Bis (3,5-dimethyl-4-hydroxyphenyl) sulfone,
2,4-bis (3,5-dimethyl-4-hydroxyphenyl) -2-methylbutane,
1,1-bis (3,5-dimethyl-4-hydroxyphenyl) cyclohexane,
α , α ′ -Bis- (3,5-dimethyl-4-hydroxyphenyl) -p-diisopropylbenzene,
2,2-bis (3,5-dichloro-4-hydroxyphenyl) propane and
2,2-bis (3,5-dibromo-4-hydroxyphenyl) propane.

Particularly preferred diphenols of the formula (VII) are, for example:
2,2-bis (4-hydroxyphenyl) propane,
2,2-bis (3,5-dimethyl-4-hydroxyphenyl) propane,
2,2-bis (3,5-dichloro-4-hydroxyphenyl) propane,
2,2-bis (3,5-dibromo-4-hydroxyphenyl) propane and
1,1-bis (4-hydroxyphenyl) cyclohexane.

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

The other diphenols can be used both individually and in Mixture can be used.

The molar ratio of those to be used according to the invention Diphenols of the formula (I) to those which may also be used other diphenols, for example those of formula (VII), should be between 100 mol% (I) to 0 mol%  other diphenol and 2 mol% (I) to 98 mol% of others Diphenol, preferably between 100 mol% (I) to 0 mol% other diphenol and 5 mol% (I) to 95 mol% other Diphenol and in particular between 100 mol% (I) to 0 mol% other diphenol and 10 mol% (I) to 90 mol% of other diphenol and 10 mol% (I) to 90 mol% of other diphenol and very particularly between 100 mol% (I) to 0 mol% of others Diphenol and 20 mol% (I) to 80 mol% of other diphenol lie.

The high molecular weight polycarbonates from the inventive Diphenols of formula (I), optionally in combination with other diphenols, can according to the known Polycarbonate manufacturing processes are produced. The various diphenols can both linked statistically and in blocks be.

The present invention thus also relates to Process for the production of high molecular, thermoplastic, aromatic polycarbonates from diphenols, optionally chain breakers and optionally branching devices according to the known methods of polycarbonate production, preferably by the two-phase interface method, which is characterized in that diphenols are those 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% and very special 100 mol% to 20 mol%, based on each Total molar amount of diphenols used.  

If used, small amounts, preferably amounts between 0.05 and 2.0 mol% (based on diphenols used) of three- or more than three-functional compounds, in particular those with three or more than three, serve as branching agents, if known phenolic hydroxyl groups to obtain branched polycarbonates. Some of the compounds that can be used have three or more than three phenolic hydroxyl groups
Phloroglucin,
4,6-dimethyl-2,4,6-tri- (4-hydroxyphenyl) -hepten-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'-methylbenzyl) -4-methylphenol,
2- (4-hydroxyphenyl) -2- (2,4-dihydroxyphenyl) propane,
Hexa- (4- (4-hydroxyphenyl-isopropyl) phenyl) orthoterephthalic 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 tri-functional compounds are 2,4-dihydroxybenzoic acid, trimesic acid, cyanuric chloride and 3,3-bis (3-methyl-4-hydroxyphenyl) -2-oxo-2,3-dihydroindole.  

As a chain terminator for regulating the molecular weight serve monofunctional compounds in a known manner in usual concentrations. Suitable compounds are e.g. B. phenol, tert-butylphenols or other alkyl-C₁-C₇-substituted Phenols. For regulating the molecular weight are especially small amounts of phenols Formula (VIII) is suitable

wherein R represents a branched C₈ and / or C₉ alkyl radical. The proportion of CH₃ protons in the alkyl radical R is preferred between 47 and 89% and the share of CH and CH₂ protons between 53 and 11%; also preferred R is in the o- and / or p-position to the OH group and especially prefers the upper limit of the ortho component 20%. The chain terminators are generally in Amounts of 0.5 to 10, preferably 1.5 to 8 mol%, based on diphenols used.

The polycarbonates according to the invention can preferably using the phase boundary method (see H. Schnell, "Chemistry and Physics of Polycarbonates", polymer Reviews, Vol. IX, page 33ff, Interscience Publ., 1964) are produced in a manner known per se. The diphenols of the formula (I) are aqueous alkaline phase dissolved. For the production of copolycarbonates with other diphenols are mixtures of Diphenols of the formula (I) and the other diphenols, for example those of the formula (VII) used. To  Regulation of molecular weight can be chain terminators e.g. B. the formula (VIII) are added. Then is in the presence of an inert, preferably polycarbonate dissolving organic phase with phosgene implemented the method of phase interface condensation. The reaction temperature is between 0 ° C and 40 ° C.

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

In addition to the diphenols of the formula (I) and the other diphenols (VII) can also have their mono- and / or bis-chlorocarbonic acid esters can also be used, these being added dissolved in organic solvents will. The amount of chain terminators as well Branching then depends on moles of diphenolate structural units of (I) and, if applicable, of other di-phenols such as from (VII); as well can with the use of chlorinated carbonic acid esters Amount of phosgene reduced accordingly in a known manner will.

Suitable organic solvents for the solution of the Chain breaker and, if necessary, for the branch and the chlorocarbonic acid esters are, for example Methylene chloride, chlorobenzene, acetone, acetonitrile  and mixtures of these solvents, especially mixtures from methylene chloride and chlorobenzene. Possibly can use the chain terminators and branching be solved in the same solvent.

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

For example, serves as the aqueous alkaline phase aqueous NaOH solution.

The production of the polycarbonates according to the invention The phase interface method can be used in the usual way by catalysts such as tertiary amines, in particular tertiary aliphatic amines such as tributylamine or triethylamine be catalyzed; the catalysts can in amounts of 0.05 to 10 mol%, based on moles diphenols used. The catalysts can before the start of phosgenation or during or can also be added after phosgenation.

The isolation of the polycarbonates according to the invention takes place in a known manner.

The high molecular weight, thermoplastic, Aromatic polycarbonates can also be made after the known process in homogeneous phase, the so-called "Pyridine process", as well as according to the known  Melt transesterification process using, for example Diphenyl carbonate instead of phosgene getting produced. Again, the invention Polycarbonates isolated in a known manner.

Those obtainable by the process according to the invention Polycarbonates preferably have molecular weights w (weight average, determined by gel chromatography prior calibration) of at least 10,000, particularly preferred from 10,000 to 200,000 and especially from 20,000 to 80,000. They can be linear or branched be, they are homopolycarbonates or copolycarbonates based on the diphenols of the formula (I).

The present invention thus also relates to high molecular, thermoplastic, aromatic polycarbonates with w (weight average molecular weights) of at least 10,000, preferably from 10,000 to 200,000 and in particular from 20,000 to 80,000, available from the inventive method from diphenols of the formula (I) which are linear or branched.

The present invention thus also relates to high molecular, thermoplastic, aromatic polycarbonates with w (weight average molecular weights) of at least 10,000, preferably from 10,000 to 200,000 and especially from 20,000 to 80,000, the bifunctional Carbonate structural units of the formula (Ia)  

wherein
X, R¹, R², R³, R⁴ and m have the meaning given for the formula (I),
in amounts of 100 mol% to 2 mol%, preferably in amounts of 100 mol% to 5 mol% and in particular in amounts of 100 mol% to 10 mol% and very particularly 100 mol% to 20 mol -%, based on the total amount of 100 mol% of difunctional carbonate structural units in the polycarbonate.

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

thus in amounts from 0 mol% (inclusive) to 98 mol% including, preferably from 0 mole% to 95 mole% and in particular from 0 mol% to 90 mol% and very particularly preferably 0 mol% to 80 mol%, based in each case to the total amount of 100 mol% of difunctional Carbonate structural units in polycarbonate.

Polycarbonates based on cycloaliphatic bisphenols are generally known and z. B. in EP-01 64 476, DE-OS 33 45 945, DE-OS 20 63 052, FR 14 27 998, WP 80 00 348, BE 7 85 189. they often have relatively high freezing temperatures, however other important physical properties such as UV and Thermal aging stability is insufficient.

It has now surprisingly been found that, as already mentioned, the incorporation of the diphenols of the formula (I) according to the invention gives new polycarbonates with high heat resistance, which also have a good property profile. This applies in particular to the polycarbonates based on the diphenols (I) in which “m” is 4 or 5, and very particularly to the polycarbonates based on the diphenols (Ib)

wherein
R¹ and R² independently of one another have the meaning given for formula (I) and are particularly preferably hydrogen.

The invention thus preferably relates to polycarbonates in which the structural units of the formula (Ia) are restricted to m = 4 or 5 and very particularly those of the formula (Ic)

wherein
R¹ and R² have the meaning given for formula (Ia), but are particularly preferably hydrogen.

These polycarbonates based on the diphenols of the formula (Ib), in which, in particular, R1 and R2 are hydrogen, also have a high heat resistance good UV stability and good flow behavior in the Melt what was not to be expected.

By any combination with other diphenols, in particular with those of the formula (VII) also the polycarbonate properties in a favorable manner vary.  

The isolation of the process according to the invention available polycarbonates is done in a known manner, by obtaining those from interfacial processes separates organic phase, neutral and electrolyte-free washes and then, for example, via an evaporation extruder isolated as granules.

The polycarbonates according to the invention can still be used or after processing that for thermoplastic Additives customary in polycarbonates, such as stabilizers, Mold release agents, pigments, flame retardants, antistatic agents, Fillers and reinforcing materials in the usual amounts are added.

In particular, soot, kieselguhr, Kaolin, clays, CaF₂, CaCO₃, aluminum oxides, glass fibers and inorganic pigments both as fillers and be added as a nucleating agent and as a mold release agent for example glycerol stearates, pentaerythritol tetrastearate and trimethylol propentristearate.

The polycarbonates according to the invention can form molded articles processed by, for example the polycarbonates isolated in a known manner Granules extruded and these granules if necessary after adding the above additives by injection molding processed to various articles in a known manner.  

The polycarbonates according to the invention are in the form of moldings can be used wherever the previously known polycarbonates were used, i.e. in the electrical sector as well in the construction sector for covers and glazing, and this is when increased heat resistance good processability at the same time, i.e. if complicated Components with high heat resistance are required will.

In the examples B.1 to B.5 below, the relative viscosity measured on 0.5 wt .-% solution of the polycarbonate in CH₂Cl₂.

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

Example B.1

30.94 g (0.1 mol) of the diphenol (II), 33.6 g (0.6 mol) KOH and 560 g of water are in an inert gas atmosphere dissolved with stirring. Then you add a solution of 0.188 g (2 mol%) of phenol in 560 g of methylene chloride. In the well-stirred solution were at pH 13 to 14 and 21 to 25 ° C 19.8 g (0.2 mol) of phosgene introduced. After that 0.1 ml of ethyl pyridine is added and another 45 minutes touched. The bisphenolate-free aqueous phase is separated off, the organic phase after acidification with phosphoric acid washed neutral with water and solvent exempted. The polycarbonate showed a relative solution viscosity of 1,259.

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

Example B.2

68.4 g (0.3 mol) bisphenol A (2,2-bis (4-hydroxyphenyl) propane, 217.0 g (0.7 mol) diphenol (II), 336.6 g (6 mol) KOH and 2700 g of water are in an inert gas atmosphere dissolved with stirring. Then you add a solution of 1.88 g (0.02 mol) of phenol in 2500 g of methylene chloride. In the well-stirred solution were at pH 13 to 14 and 21 to 25 ° C 198 g (2 mol) of phosgene introduced. After that 1 ml of ethyl piperidine is added and the mixture is stirred for a further 45 min. The bisphenolate-free aqueous phase is separated off, the organic phase after acidification with phosphoric acid washed neutral with water and solvent  exempted. 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) Bisphenol A and 155 g (0.5 mol) diphenol (II) for Polycarbonate implemented.

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) Bisphenol A and 93 g (0.3 mol) diphenol (II) for Polycarbonate implemented.

The polycarbonate showed a relative solution viscosity of 1,437.

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

Example B.5

31.0 g (0.1 mol) of diphenol (II), 24.0 g (0.6 mol) of NaOH and 270 g of water are in an inert gas atmosphere dissolved with stirring. Then you add a solution of 0.309 g (1.5 mol%) of 4- (1,3-tetramethylbutyl) phenol in 250 g of methylene chloride. In the well stirred solution 19.8 g (0.2 mol) were at pH 13 to 14 and 21 to 25 ° C. Phosgene introduced. Then 0.1 ml of ethyl piperidine added and stirred for a further 45 min. The bisphenolate-free aqueous phase is separated off, the organic phase after Acidify with phosphoric acid washed neutral with water and freed from the solvent. The polycarbonate showed a relative solution viscosity of 1.314.

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

To estimate the UV resistance of the new polycarbonates became the primary radical formation under UV radiation with a mercury vapor lamp (edge filter 305 nm) compared to a polycarbonate based on the 2.2 Bis- (4-hydroxyphenyl) propane determined. It was found, that the polycarbonate according to Example B.1 is less Primary radical formation rate and therefore a higher UV resistance having.

Claims (15)

1. Dihydroxydiphenylcycloalkanes of the formula wherein
R¹ and R² independently of one another are hydrogen, halogen, C₁-C₈-alkyl, C₅-C₆-cycloalkyl, C₆-C₁₀-aryl and C₇-C₁₂-aralkyl,
m is an integer from 4 to 7,
R³ and R⁴ individually selectable for each X, independently of one another hydrogen, C₁-C₆-alkyl and
X is carbon
with the proviso that on at least one atom X R³ and R⁴ simultaneously mean alkyl. 2. Dihydroxydiphenylcycloalkanes of formula (I) according to claim 1, characterized in that in formula (I) both to C-1 α -X atoms are not dialkyl-substituted. 3. Dihydroxydiphenylcycloalkanes of formula (I) according to claim 2, characterized in that in formula (I) is a dialkyl-substituted X atom in the β- position to C-1. 4. Dihydroxydiphenylcycloalkanes of formula (I) according to claim 1, characterized in that "m" is 4 or 5. 5. 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane. 6. Process for the preparation of the dihydroxydiphenylcycloalkanes of the formula (I) wherein
X, R¹, R², R³, R⁴ and m have the meaning given in claim 1,
characterized in that phenols of the formula (V) wherein
R¹ and R² have the meaning given for formula (I),
with ketones of the formula (VI) wherein
X, m , R³ and R⁴ have the meaning given for formula (I),
in a molar ratio (V): (VI) between 2: 1 and 10: 1, preferably between 2.5: 1 and 6: 1 at temperatures between -30 ° C and 300 ° C, preferably between -15 ° C and 150 ° C, and at pressures from 1 to 20 bar, preferably from 1 to 10 bar, in the presence of acidic catalysts and optionally in the presence of co-catalysts and / or solvents and / or dehydrating agents. 7. Use of the diphenols of the formula (I) Claim 1 for the production of high molecular weight, thermoplastic, aromatic polycarbonates.   8. Process for the production of high molecular weight thermoplastic, aromatic polycarbonates Diphenols, optionally chain terminators and optionally Branch according to the known methods the polycarbonate production, preferably after the two-phase interface method, characterized in that that as diphenols those of the formula (I) of claim 1 in amounts of 100 mol% to 2 mol%, based on the total molar amount Diphenols used. 9. High molecular weight, thermoplastic, aromatic polycarbonates with w (weight average molecular weights) of at least 10,000, obtainable by the process of claim 8. 10. High molecular weight, thermoplastic, aromatic polycarbonates with w (weight average molecular weights) of at least 10,000, preferably from 10,000 to 200,000 and in particular from 20,000 to 80,000, the bifunctional carbonate structural units of the formula (Ia) wherein
X, R¹, R², R³, R⁴ and m have the meaning given for the formula (I) of claim 1,
in amounts of 100 mol% to 2 mol%, based on the total amount of 100 mol% of difunctional carbonate structural units in the polycarbonate. 11. Polycarbonates according to claim 10, characterized in that that the carbonate structural units of the Formula (Ia) in amounts of 100 mol% to 5 mol% contain. 12. Polycarbonates according to claims 10 and 11, characterized in that they are 100 mol% complementary amounts of other difunctional carbonate structural units of the formula (VIIa) contain, in which -OZO- is. 13. Polycarbonates according to claim 10, characterized in that "m" is 4 or 5. 14. Polycarbonates according to claim 10, characterized in that the structural units of the formula (Ia) are those of the formula (Ic) are what
R¹ and R² have the meaning given for formula (Ia) of claim 10. 15. Polycarbonates according to claim 14, characterized in that that R1 and R2 are hydrogen.