DE3930673A1 - Stabilised polycarbonate(s) with bifunctional carbonate units - contg. sec. di:arylamine(s) with sec. di:arylamine structural units useful in moulding articles with improved toughness and properties - Google Patents

Abstract

Stabilised polycarbonates (I) (MW of at least 10000) contg. 100 mol. % bifunctional carbonate structural units of formula (Ia), R1 and R2 = independently H, halogen, 1-8C alkyl, 5-6-cycloalkyl, 6-10C aryl, 7-12C aralkyl, m = 4-7, R3 and R4 for every x individually and independently and R3 and R4 must both = alkyl for X atom(s). The novelty is that (I) contain 0.01-5 wt. % sec. diarylamines with 1-30 sec. diarylamine structural units. Prepn. of (I) is also claimed in which (I) contg. bifunctional carbonate structural units of formula (Ia) are mixed with sec. amines contg. 0.01-5 wt. % 1-30 sec. diacrylamine structural units over the soln. or melt, and opt. after evapn. of the solvent, are granulated or processed directly to mouldings. USE/ADVANTAGE - (I) are used in fibres, foils, plates, injection and extrusion moulding articles. (I) have improved toughness. The optical properties (e.g. transmission) of (I) are improved by hot air storage.

Description

Subject of the invention of the German patent application P 38 32 396.6 (Le A 26 344) are 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.

Preferred are at 1-2 atoms X, in particular only on an atom X, R³ and R⁴ simultaneously alkyl. More preferred Alkyl is methyl; the X atoms in the α position to the di-phenyl-substituted carbon atom (C-1) are preferred not dialkyl-substituted, but alkyl disubstitution preferred in the β-position to C-1.

In particular, the invention relates to dihydroxydiphenylcycloalkanes with 5 and 6 ring carbon atoms in cycloaliphatic Rest (m = 4 or 5 in formula (I) as for example the diphenols of the formulas

and

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

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, Ullmanns Encyclopedia of Chemical Engineering 4th revised and extended edition volume 15, pages 61-77, publisher Chemie-Weinheim-New York 1978; for chlorophenols, Ullmanns 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 4431 ff, J. Am. Chem. Soc. 87, (1965), Pages 1353 ff, 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-trimethylcyclopentanone, 2,4,4-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, 2,5,5-trimethylcyclohexanone, 3,3,5-trimethylcyclohexanone, 3,4,4-trimethylcyclohexanone, 2,3,3,4-tetramethylcyclopentanone, 2,3,4,4-tetramethylcyclopentanone, 3,3,4,4-tetramethylcyclopentanone, 2,2,5-trimethylcycloheptanone, 2,2,6-trimethylcycloheptanone, 2,6,6-trimethylcycloheptanone, 3,3,5-trimethylcycloheptanone, 3,5,5-trimethylcycloheptanone, 5-ethyl-2,5-dimethylcycloheptanone, 2,3,3,5-tetramethylcycloheptanone, 2,3,5,5-tetramethylcycloheptanone, 3,3,5,5-tetramethylcycloheptanone, 4-ethyl-2,3,4-trimethylcyclopentanone, 2-isopropyl-4,4-dimethylcyclopentanone, 4-isopropyl-2,4-dimethylcyclopentanone, 2-ethyl-3,5,5-trimethylcyclohexanone, 3-ethyl-3,5,5-trimethylcyclohexanone, 3-ethyl-4-isopropyl-3-methyl-cyclopentanone, 4-sec. Butyl-3,3-dimethylcyclopentanone, 2-isopropyl-3,3,4-trimethylcyclopentanone, 3-ethyl-4-isopropyl-3-methyl-cyclohexanone, 4-ethyl-3-isopropyl-4-methyl-cyclohexanone, 3-sec-butyl-4,4-dimethylcylohexanone, 3-isopropyl-3,5,5-trimethylcyclohexanone, 4-isopropyl-3,5,5-trimethylcyclohexanone, 3,3,5-trimethyl-5-propylcyclohexanone, 3,5,5-trimethyl-5-propylcyclohexanone,  2-butyl-3,3,4-trimethylcyclopentanone, 2-butyl-3,3,4-trimethylhexanone, 4-butyl-3,3,5-trimethylcyclohexanone, 3-isohexyl-3-methylcyclohexanone, 5-ethyl-2,4-diisopropyl-5-methylcyclohexanone, 2,2-dimethylcyclooctanone, and 3,3,8-trimethylcyclooctanone.

Examples of preferred ketones are

Bisphenol production generally uses 2 to 10 Moles, 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 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 cocatalysts and / or solvents and / or dehydrating agents.

Preferred in formula (I) are 1-2 atoms X, in particular alkyl on only one atom X, R³ and R Alkyl at the same time. The preferred alkyl radical is methyl; also usable are ethyl or C₃-C₆-alkyl radicals that are straight-chain or can be branched. The X atoms in α position to the di-phenyl-substituted C atom (C-1) are preferably not dialkyl-substituted, but is 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 referenced in 1964. Sometimes the reaction by choosing appropriate catalysts and reaction conditions can be controlled so that the desired Connection fails or crystallizes out of what their Insulation made easier.  

Example A Preparation of diphenol (II)

7.5 mol (705 g) of phenol and 0.15 mol (30.3 g) of dodecyclthiol are placed in a 1 liter round-bottom flask equipped with a stirrer, dropping funnel, thermometer, reflux condenser and gas inlet tube and at 28 to 30 ° C. with dry HCl -Gas saturated. A solution of 1.5 mol (210 g) dihydroisophorone (3,3,5-trimethyl-cyclohexan-1-one) and 1.5 mol (151 g) phenol are added dropwise to this solution within 3 hours, with HCl -Gas is fed through the reaction solution. When the addition has ended, HCl gas is passed in for a further 5 hours. The mixture is left to react for 8 h at room temperature. The excess phenol is then removed by steam distillation. The remaining residue is extracted twice with petroleum ether (60-90) and once with methylene chloride and filtered off.
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, 22 11 956, 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.

Diphenols of the formula (VII) are particularly preferred 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 particularly 100 mol% to 20 mol%, based on each Total molar amount of diphenols used.  

If used, serve as branching in a known manner small amounts, preferably amounts between 0.05 and 2.0 mol% (based on diphenols used), on three or more than three-functional compounds, in particular those with three or more than three phenolic Hydroxyl groups to obtain branched polycarbonates. Some of the three or usable connections are 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 33 ff., 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 are 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" and 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 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),
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.

Surprisingly, it has now been shown that how already mentioned by installing the invention Diphenols of formula (I) new polycarbonates with high Heat resistance can be obtained, which otherwise have a good property profile. This is especially true for the polycarbonates based on the diphenols (I), in where "m" is 4 or 5, and especially for the polycarbonates based on 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 are 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 Common polycarbonate additives such as stabilizers, mold release agents, Pigments, flame retardants, antistatic agents, Fillers and reinforcements 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 trimethylolpropane tristearate.

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 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 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) to 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) to 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 protect 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 2,2-bis (4-hydroxyphenyl) propane certainly. It was found, that the polycarbonate according to Example B1 is less Primary radical formation rate and therefore a higher UV resistance having.  

It has now been shown that the polycarbonates are based of bisphenols of formula (I) under the conditions of thermal and oxidative stress, i.e. under the Influence of air reduced at elevated temperatures be what results in a deterioration in mechanical Characteristics manifested. In addition, the optical Properties (e.g. transmission) deteriorate and you see color changes.

It is known to use aromatic polycarbonates with stabilizers protect against thermooxidative damage. Sterically hindered phenols are commonly used (cf. Taschenbuch der Kunststoffadditive, ed. V. R. Gächter, H. Müller, C. Hauser Verlag Munich, Vienna 1983, p. 73).

Surprisingly, it has now been found that the polycarbonates based on the diphenols of the formula (I) the addition of secondary diarylamines with 1 to 30 secondary Diarylamine structural units, preferably from those of the formula (IX)

wherein "n" is an integer from 0 to 29, preferably from 1 to 29, in particular from 1 to 19 and particularly preferably from 1 to 10, wherein
E is hydrogen, branched C₄-C₉-alkyl, C₇-C₁₅-aralkyl or C₅-C₁₂-cycloalkyl and is ortho or para to the secondary amino group, with the exception that in the case of "n" equals zero, E is not hydrogen
R⁵ H, CH₃, C₂H₅ or -CH (CH₃) ₂ and E 'the rest

with the meanings given above for E and R⁵, and wherein
-Y- a double-bonded hydrocarbon residue selected from Y₁ to Y₈

Preferred diarylamines are diphenylamines (IX) with 2 to 30 secondary diphenylamine structural units, wherein R⁵ Is H or CH₃, in particular H.

Preferred C₇-C₁₅ aralkyl radicals E include alkyl-substituted Aralkyl radicals and are, for example (E1) to (E8).

Particularly preferred compounds of the formula (IX) are those with E = hydrogen.

The present invention relates to stabilized Polycarbonates of German patent application P 38 32 396 (Le A 26 344), which are characterized in that they a content of 0.01% by weight to 5% by weight, preferably from 0.02% by weight to 2% by weight and in particular from 0.03% by weight up to 1.0% by weight, based on the weight of polycarbonate, on the diarylamines according to the invention, particularly preferred contain compounds of formula (IX).

The polycarbonates according to the invention are notable for improved toughness, furthermore the optical Properties (e.g. transmission) after hot air storage improved.

Preferred polycarbonates according to the present invention are also the preferred according to German patent application P 38 32 396.6 (Le A 26 344); this also applies to the particularly preferred polycarbonates of the formula (Ic).

The diarylamines to be used according to the invention and their manufacture is known (see for example EP-OS 00 84 108 (Le A 21 312)).

In this reference, they are for stabilization used by polyamides.

The transfer to stabilize polycarbonates was not obvious, since it is known that polycarbonates secondary amines are degraded, d. H. the carbonate group is split.

Examples of particularly preferred diarylamine compounds are:

and

where n is an integer from 1 to 5. Most notably (IXa) and (IXb) with n = 1 are preferred.

The incorporation of the stabilizers according to the invention in the thermoplastic polycarbonates, for example done by entering the calculated amount stabilizer in a solution of the stabilized Polycarbonates, evaporation of the solution and removal of Residual amounts of solvent in an evaporation extruder. Man can also be a solution of the stabilizer in an inert Solvents such as toluene, xylene, acetone, isopropanol, Ethyl acetate, butyl acetate and the like. a. on polycarbonate granulate spin up, dry and then in an extruder, kneader or other mixing devices the intimate mixing of stabilizer with polycarbonate. The same a powder stabilizer on polycarbonate spin on and then mix in the snail. A larger amount of 1-10% by weight can also be preferred 2-8 wt .-%, particularly preferably 3-7 wt .-% stabilizer mix in the extruder with polycarbonate, granulate and the granules of this concentrate in corresponding Quantities e.g. B. continuously via dosing scales a polycarbonate meter in and via extruders, especially in the twin-screw extruder add the polycarbonate so that a polycarbonate provided with the desired amount of stabilizer is obtained. This latter practice is preferred for continuous operation.

The present invention thus also relates to a Process for the preparation of the stabilized invention Polycarbonate, which is characterized by  that the polycarbonates of the German patent application P 38 32 396.6 with the secondary diarylamines according to the invention with 1 to 30 secondary diarylamine structural units in amounts of 0.01 to 5% by weight, preferably 0.02 to 2% by weight and in particular 0.03 to 1.0% by weight, based on weight polycarbonate, via the solution or Melt, especially in extruders, especially in twin-screw extruders, mixed in a known manner and then optionally after evaporation of the solvent, granulated or directly to shaped bodies in known Further processed.

The stabilized polycarbonates according to the invention can be used for fibers, foils, sheets, injection and extrusion articles processed as this in the German patent application P 38 32 396.6 (Le A 26 344) or in the German patent application P 38 37 090.5 (Le A 26 402) and in the German patent application P 39 09 601.7 (Le A 26 699) is. These are generally known processing methods.

Examples of objects are plates or multi-wall sheets, Headlight lamps and reflectors.

Examples

The bisphenol of the formula (II) was prepared according to the information in the German patent application P 38 33 953.6.

Polycarbonate A)

According to the information in the German patent application P 38 33 953.6 was a copolycarbonate based on 55 mol% of the bisphenol of the formula (II) and 45 mol% 2,2-bis (4-hydroxyphenyl) propane with 4- (1,1,3,3-tetramethylbutyl) phenol as a chain terminator according to the procedure the interfacial polycondensation. The rel. Solution viscosity was 1.30.

The following were used as diphenylamine compounds:

Compounds (IXa) (cf. EP 00 84 108, example 16):

Compound mixture (IXc) (cf. EP = 0 84 108, example 5, polymer mixture):

with n = 1-5

The amounts of diphenylamine compounds given in the table were at temperatures of 340 ° C on a twin-screw extruder into the polycarbonates incorporated and the extrudate granulated. On a usual injection molding machine were test specimens of dimensions Made 80 × 10 × 4 mm. The storage took place in a convection oven at temperatures of 150 ° C ± 5 ° C. After the specified times, the test specimens taken. The rel. Solution viscosity and the Impact strength (according to ISO 1-C) determined. The relative Solution viscosity was in CH₂Cl₂ to 0.5 wt .-% Solutions that measured polycarbonates at 250 ° C.

Table 1

Table 2

The examples show that the solution viscosity of the stabilized settings drops significantly less and improved toughness values after furnace storage exhibit. This is surprising since polycarbonates are under the influence of amines otherwise a decrease in solution viscosity demonstrate.

Claims (3)

1. Stabilized polycarbonates with w (weight average molecular weights) of at least 10,000, the bifunctional carbonate structural units of the formula (Ia) 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 or C₁-C₆-alkyl and
X is carbon,
with the proviso that on at least one atom X R³ and R⁴ simultaneously mean alkyl,
in amounts of 100 mol%, based on the total amount of 100 mol% of difunctional carbon structural units in the polycarbonate, characterized in that they have a content of 0.01% by weight to 5% by weight by weight polycarbonate, containing secondary diarylamines with 1 to 30 secondary diarylamine structural units. 2. Stabilized polycarbonates of claim 1, characterized in that the diarylamines correspond to the formula (IX) wherein
n is an integer from 0 to 29,
E is hydrogen, branched C₄-C₉-alkyl, C₇-C₁₅-aralkyl or C₅-C₁₂-cycloalkyl and is ortho or para to the secondary amino group, with the exception that in the case of "n" equals zero, E is not hydrogen
R⁵ is H, CH₃, C₂H₅ or -CH (CH₃) ₂ and
E ′ the rest with the meanings given above for E and R⁵, and wherein
-Y- a double-bonded hydrocarbon residue selected from Y₁ to Y₈ is. 3. Process for the preparation of the polycarbonates Claims 1 and 2, characterized in that the polycarbonates defined in claim 1, the bifunctional carbonate structural units of Contain formula (Ia) with secondary diarylamines with 1 to 30 secondary diarylamine structural units in amounts of 0.01 to 5 wt .-%, based on Weight polycarbonate, over the solution or melt mixed in a known manner and then, if necessary after evaporation of the solvent, granulated or directly to shaped bodies in known Further processed.